JP7013393B2 - Additional manufacturing of rubber-like materials - Google Patents

Description

The present invention relates to, in some embodiments thereof, with respect to additive manufacturing (AM), but not particularly limited, with formulations and methods that can be used for additive manufacturing of objects made from rubbery materials, at least in part.

Synthetic rubber is generally made from artificial elastomers. Elastomers are viscoelastic polymers, which generally exhibit low Young's modulus and high yield strain compared to other materials. Elastomers are amorphous polymers that are generally present above their glass transition temperature, so significant partial motion is possible. At ambient temperature, the rubber is relatively soft, has elasticity of about 3 Mpa, and is deformable.

Elastomers are usually thermosetting polymers (or copolymers), which require curing (vulcanization) to crosslink the polymer chains. Elasticity derives from the ability of long chains to reconstruct themselves to disperse the applied stress. Covalent cross-linking ensures that the elastomer returns to its original shape when stress is removed. Elastomers generally grow reversibly from 5% to 700%.

Rubbers usually further contain fillers or reinforcing agents for the purpose of increasing their hardness. The most common reinforcing agents include finely divided carbon black and / or finely ground silica.

Both carbon black and silica, when added to the polymer mixture during rubber production, generally increase the elastic modulus of the rubber 2-3 times at a concentration of about 30% by volume, and also provide significant toughness, especially abrasion resistance. , Otherwise give a weak material. If a larger amount of carbon black or silica particles is added, the modulus of elasticity may increase, but the tensile strength may decrease.

Addition manufacturing is generally a method in which a three-dimensional (3D) object is manufactured using a computer model of the object. Such methods have been used in various fields such as design-related fields for visualization, demonstration and mechanical prototyping, as well as rapid production (RM) purposes.

The basic operation of any AM system consists of slicing the 3D computer model into thin cross sections, converting the results into 2D position data, and supplying the data to the controller that manufactures the 3D structure in layers.

There are various AM technologies, including stereolithography, digital light processing (DLP), and three-dimensional (3D) printing (especially 3D inkjet printing). Such techniques are generally carried out by layer-by-layer deposition and solidification of one or more construction materials, generally photopolymerizable (photocurable) materials.

In a three-dimensional printing process, for example, the construction material is ejected from an ejection head with a set of nozzles, depositing layers on the support structure. Depending on the construction material, the layer can then be cured or solidified using suitable equipment.

There are various 3D printing technologies, such as US Pat. Nos. 6,259,962, 6,569,373, 6,658,314, 6,850,334, 7,183. Nos. 335, 7,209,797, 7,225,045, 7,300,619, 7,479,510, 7,500,846, 7,962,237 And No. 9,031,680. They are all the same applicant and their contents are incorporated here for reference.

The printing system used for additive manufacturing can include a receiving medium and one or more print heads. The receiving medium can be, for example, a production tray that can include a horizontal plane for supporting the material ejected from the print head. The print head can be, for example, an inkjet head having a plurality of ejection nozzles arranged in an array of one or more rows along the longitudinal axis of the print head. The printhead can be positioned so that its longitudinal axis is substantially parallel to the indicated direction. The printhead is a controller such as a microprocessor that controls the printing process, including the movement of the printhead according to a predefined scan scheme (CAD configuration converted to stereolithographic (STL) format and programmed into the controller). Can be further included. The print head can include a plurality of jet nozzles. The injection nozzle ejects the material onto the receiving medium to form a layer that represents the cross section of the 3D object.

In addition to the printhead, there may be a curing energy source for curing the ejected construction material. The curing energy is generally radiation, such as UV radiation.

In addition, the printing system can include a leveling device for leveling and / or establishing the height of each layer after deposition and at least after partial solidification and prior to layer deposition.

Construction materials can include modeling materials and supporting materials, which form the object, and a temporary support structure that supports the object so that the object is constructed.

The modeling material (which can contain one or more materials) is deposited to produce the desired object, and the supporting material (which can contain one or more materials) is the modeling material element. Used with or without, to provide a support structure for a particular area of the object at construction, for example if the object contains protruding features or shapes such as curved geometry, negative angles, gaps, etc. , Ensuring proper vertical placement of continuous object layers.

It is preferred that both the modeling material and the supporting material are liquid at the working temperature at which they are ejected and then generally cured when exposed to curing energy (eg UV curing) to form the required layer shape. After printing is complete, the support structure is removed and the final shape of the manufactured 3D object appears.

Multiple addition manufacturing processes allow the addition formation of objects using more than one type of modeling material. For example, the publication No. of the applicant. A U.S. patent application with 2010/01/91360 controls a solid free-form fabrication device with multiple ejection heads, a construction material supply device configured to supply multiple construction materials to the fabrication device, and a fabrication device and supply device. Disclose a system that includes a control unit configured to do so. The system has multiple modes of operation. In one mode, all ejection heads operate during a single construction scan cycle of the fabrication equipment. In another mode, one or more of the ejection heads do not operate during a single construction scan cycle or part thereof.

In a 3D inkjet printing process such as Polyjet (Stratasys Ltd., Israel), the building material is selectively ejected from one or more printheads and predetermined as specified by the software file. It is deposited on the production tray in continuous layers according to the composition.

U.S. Pat. No. 9,227,365 by the applicant is a solid free form of a sheathed object composed of a plurality of layers, a layered core constituting a core region, and a layered sheath constituting an outer cover region. Disclose the method and system for production.

Addition manufacturing processes are used to form rubbery materials. For example, rubbery materials are used in PolyJet (trade name) systems as described herein. These materials have a relatively low viscosity that allows ejection, for example by inkjet, and are formulated to exhibit a _Tg below room temperature, such as 10 ° C. or below. The latter is obtained by blending compounds with a relatively low degree of cross-linking and by using monomers and oligomers (eg, acrylic elastomers) with unique flexible molecular structures.

An exemplary family of rubbery materials (sold under the trade name "Tango" family) that can be used in PolyJet systems is a variety of elastomers including Shore A hardness, elongation at break, tear resistance, and tensile strength. Gives characteristics.

Rubbery materials include display and communication models; rubber enclosures and overmolding; soft-touch coatings and non-slip surfaces for touring or prototyping; and many knobs, grips, handles, handles, gaskets, seals, hoses, footwear. Useful for modeling applications.

In the conventional production of elastomeric materials (elastomers, rubbery materials), the starting material is generally a thermoplastic polymer with a low _Tg , which is formulated and cured or added to achieve the desired final properties. It is vulcanized. In contrast, in addition manufacturing processes such as 3D (inkjet) printing, the cured polymer is made in one step from suitable monomers and / or low molecular weight crosslinkers and oligomers. Controlling the molecular weight, crosslink density, and mechanical properties of the rubbery material obtained in such a process is therefore challenging. Thus, for example, PolyJet (trade name) rubbery materials are often characterized by a slow return rate after deformation and / or a low tear resistance (TR) when compared to, for example, conventional elastomers. PolyJet rubbery materials that exhibit high elongation are often characterized by low modulus, low tear resistance and / or low _Tg and low tackiness.

The present inventor has improved mechanical properties in the production of rubbery materials by using various types of nano-sized silica particles, including, for example, fine hydrophilic silica, hydrophobic silica, and acrylic coated silica. It was discovered that it produces a rubber-like material with silica. The present inventor has shown that by using such a method, a rubbery material having improved elongation, modulus, and tear resistance can be obtained at the same time.

According to some embodiments of the present invention, there is provided a method of additional manufacturing of a three-dimensional object made of an elastomeric material, wherein the method sequentially comprises a plurality of layers in a forming pattern corresponding to the shape of the object. Each formation of at least two (a few) or three (a few) layers is ejected and ejected from at least one form material formulation, comprising forming and thereby forming an object. The modeling material comprising exposing the modeling material to curing energy to form a cured modeling material, said at least one modeling material formulation comprises an elastomeric curable material and silica particles.

According to some of the embodiments described herein, silica particles have an average particle size of less than 1 micron.

According to some of the embodiments described herein, at least a portion of the silica particles comprises a hydrophilic surface.

According to some of the embodiments described herein, at least a portion of the silica particles comprises a hydrophobic surface.

According to some of the embodiments described herein, at least a portion of the silica particles comprises functionalized silica particles.

According to some of the embodiments described herein, at least a portion of the silica particles is functionalized with a curable functional group (eg, a (meth) acrylate group).

According to any part of the embodiments described herein, the amount of silica particles in the modeling material formulation is from about 1 to about 20% by weight of the total weight of the modeling material formulation containing the particles. Alternatively, it is in the range of about 1 to about 15% by weight or about 1 to about 10% by weight.

According to any part of the embodiments described herein, the amount of silica particles in the modeling material formulation is the formulation system or one or more modeling materials as described herein. It ranges from about 1 to about 20% by weight or from about 1 to about 15% by weight or from about 1 to about 10% by weight of the total weight of the formulation.

According to some of the embodiments described herein, the weight ratio of the elastomeric curable material to the silica particles ranges from about 30: 1 to about 4: 1.

According to any portion of the embodiments described herein, the amount of elastomeric curable material is at least 40% by weight or at least 50% by weight of the total weight of the modeling material formulation containing the material. ..

According to some of the embodiments described herein, the amount of elastomeric curable material is the whole of the compounding system as described herein or one or more modeling material formulations. At least 40% by weight or at least 50% by weight by weight.

According to any part of the embodiments described herein, the elastomeric curable material is a monofunctional elastomer curable monomer, a monofunctional elastomer curable oligomer, a polyfunctional elastomer curable monomer, a polyfunctional elastomer cure. It is selected from sex oligomers and any combination thereof.

According to any part of the embodiments described herein, the elastomeric curable material and the silica particles are in the same modeling material formulation.

According to some of the embodiments described herein, at least one form material formulation further comprises at least one additional curable material.

According to any part of the embodiments described herein, the additional curable material is a monofunctional curable monomer, a monofunctional curable oligomer, a polyfunctional curable monomer, a polyfunctional curable oligomer, And any combination of them.

According to some of the embodiments described herein, the elastomeric curable material, silica particles, and additional curable material are in the same modeling material formulation.

According to any part of the embodiments described herein, the discharge is of a type of modeling material formulation.

According to any part of the embodiments described herein, the discharge is for a combination of two or more modeling materials.

According to some of the embodiments described herein, the discharge is from at least two modeling material formulations, one of which comprises an elastomeric curable material. Another type of formulation contains additional curable material.

According to any part of the embodiments described herein, at least one modeling material formulation is at least one additional non-curable material (eg, colorant, initiator, dispersant, etc. It further comprises one or more of surfactants, stabilizers, and inhibitors (inhibitors).

According to any part of the embodiments described herein, the elastomeric curable material is a UV curable elastomer material.

According to some of the embodiments described herein, the curing energy comprises UV irradiation.

According to some of the embodiments described herein, the elastomeric curable material is an acrylic elastomer.

According to some of the embodiments described herein, at least one form material formulation is characterized by a tear resistance of at least 4000 N / m when cured.

According to some of the embodiments described herein, at least one type of modeling material formulation, when cured, is at least 500 N / m higher than the cured modeling material without silica particles. Characterized by tear resistance.

According to any part of the embodiments described herein, at least one form material formulation is characterized by a tensile strength of at least 2 MPa when cured.

According to any part of the embodiments described herein, at least one form material formulation consists of a hardened form material and is a tube connecting the two O-rings to the ring. It is such that an object comprising and is characterized by tear resistance under constant stretching for at least one hour or at least one day.

According to any part of the embodiments described herein, the discharge is of at least two modeling material formulations and is voxel-based, of the modeling material formulations. One type of voxel is interlaced with at least one type of voxel in another modeling material formulation.

According to some of the embodiments described herein, the discharge is of at least two modeling material formulations and at least partially encloses the core region and the core region. It is like forming one or more outer cover regions, thereby producing an object composed of a layered core constituting a plurality of layers and a core region and a layered sheath constituting the outer cover region.

According to any part of the embodiments described herein, one or more coat regions include a plurality of coat regions.

According to any part of the embodiments described herein, discharging the layer further comprises discharging the support material formulation.

According to some of the embodiments described herein, the method further comprises removing the supporting material following exposure.

According to some embodiments of the invention, a three-dimensional object made by the method described herein in any one of the respective embodiments, wherein the object comprises at least a portion comprising an elastomeric material. A three-dimensional object is provided.

According to some embodiments of the invention, as described herein in any one of the respective embodiments, one or more blending systems comprising a curable elastomeric material and silica particles. A compounding system containing the compound is provided.

According to any part of the embodiments described herein, the amount of the silica particles in the compounding system is 1 to 20% by weight or 1 to 15% by weight or 1 to 1 to the total weight of the compounding system. It is in the range of 10% by weight.

According to any part of the embodiments described herein, the weight ratio of the total weight of the elastomeric curable material to the total weight of the silica particles in the formulation ranges from 30: 1 to 4: 1. Is.

According to any portion of the embodiments described herein, the amount of elastomeric curable material in the formulation is at least 40% by weight or at least 50% by weight of the total weight of the formulation.

According to any part of the embodiments described herein, the elastomeric curable material is a monofunctional elastomer curable monomer, a monofunctional elastomer curable oligomer, a polyfunctional elastomer curable monomer, a polyfunctional elastomer cure. It is selected from sex oligomers and any combination thereof.

According to any part of the embodiments described herein, the elastomeric curable material and the silica particles are in the same formulation.

According to some of the embodiments described herein, the compounding system further comprises at least one additional curable material.

According to any part of the embodiments described herein, the additional curable material is a monofunctional curable monomer, a monofunctional curable oligomer, a polyfunctional curable monomer, a polyfunctional curable oligomer, And any combination of them.

According to some of the embodiments described herein, the elastomeric curable material, silica particles, and additional curable material are in the same formulation.

According to any part of the embodiments described herein, the compounding system comprises a type of compounding.

According to any part of the embodiments described herein, the compounding system comprises two or more formulations.

According to some of the embodiments described herein, the compounding system comprises at least two formulations, one of the formulations comprising an elastomeric curable material and another type of formulation. Includes additional curable material.

According to some of the embodiments described herein, the compounding system further comprises at least one additional non-curable material.

According to any part of the embodiments described herein, the non-curable material is a colorant, an initiator, a dispersant, a surfactant, a stabilizer, an inhibitor, and any of them. Selected from combinations.

According to any portion of the embodiments described herein, the compounding system comprises at least one elastomer monofunctional curable material, at least one elastomer polyfunctional curable material, and at least one additional simple material. Includes functionally curable materials.

According to some of the embodiments described herein, the total concentration of the monofunctional curable material is in the range of 10-30% by weight of the total weight of the formulation.

According to some of the embodiments described herein, the total concentration of the elastomer monofunctional curable material is in the range of 50-70% by weight of the total weight of the formulation.

According to some of the embodiments described herein, the total concentration of the elastomeric polyfunctional curable material is in the range of 10-20% by weight of the total weight of the formulation.

According to any part of the embodiments described herein, the total concentration of the monofunctional curable material is 10-30% by weight of the total weight of the formulation of the elastomeric monofunctional curable material. The total concentration is 50 to 70% by weight of the total weight of the compounding system, and the total concentration of the elastomer polyfunctional curable material is 10 to 20% by weight of the total weight of the compounding system.

According to some of the embodiments described herein, the total concentration of the monofunctional curable material is in the range of 20-30% by weight of the total weight of the formulation.

According to some of the embodiments described herein, the total concentration of the elastomer monofunctional curable material is in the range of 30-50% by weight of the total weight of the formulation.

According to some of the embodiments described herein, the total concentration of the elastomeric polyfunctional curable material is in the range of 10-30% by weight of the total weight of the formulation.

According to some of the embodiments described herein, the total concentration of the monofunctional curable material is 20-30% by weight of the total weight of the compounding system of the elastomeric monofunctional curable material. The total concentration is 30 to 50% by weight of the total weight of the compounding system, and the total concentration of the elastomer polyfunctional curable material is 10 to 30% by weight of the total weight of the compounding system.

According to any part of the embodiments described herein, the elastomeric curable material is a UV curable elastomer material.

According to some of the embodiments described herein, the elastomeric curable material is an acrylic elastomer.

According to any part of the embodiments described herein, a blending system as described herein in any of the respective embodiments is a three-dimensional object as a modeling material blending system. It is intended for use in additional manufacturing.

According to aspects of some embodiments of the invention, kits comprising the formulations described herein in any of the respective embodiments are provided.

According to some of the embodiments described herein, the formulation system comprises at least two formulations, each of which is individually packaged within a kit.

According to some of the embodiments described herein, the compounding system provides a material characterized by a tear resistance of at least 4000 N / m when cured.

According to some of the embodiments described herein, the compounding system, when cured, is a material characterized by a tear resistance that is at least 500 N / m higher than the cured material without silica particles. give.

According to some of the embodiments described herein, the compounding system, when cured, provides a material characterized by a tensile strength of at least 2 MPa.

According to any part of the embodiments described herein, an object consisting of a cured formulation and comprising two O-rings and a tube connecting the rings is at least one hour. Or characterized by tear resistance under constant stretching for at least one day.

Unless otherwise defined, all technical and / or scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which the invention belongs. Methods and materials similar to or equivalent to the methods and materials described herein can be used in the practice or testing of the present invention, but exemplary methods and / or materials are described below. In the event of a conflict, the present patent specification, including the definition, will prevail. In addition, the materials, methods and examples are illustrative only and are not intended to be limiting.

Performing the methods and / or systems of the embodiments of the present invention includes performing or completing selected tasks manually, automatically or in combination thereof. In addition, a number of selected steps can be performed by hardware, software, or firmware, or a combination thereof using an operating system, depending on the actual equipment or device of the methods and / or embodiments of the system of the invention.

For example, the hardware for performing selected tasks according to embodiments of the present invention can be implemented as chips or circuits. As software, the tasks selected by embodiments of the present invention can be performed as software, such as instructions of multiple software performed by a computer using an appropriate operating system. In an exemplary embodiment of the invention, one or more tasks according to the exemplary embodiments of the methods and / or systems described herein are performed on a data processor, eg, a computing platform that executes multiple instructions. Will be done. Optionally, the data processor is a volatile memory for storing instructions and / or data, and / or a non-volatile storage device for storing instructions and / or data (eg, a magnetic hard disk and / or). Detachable recording medium) is included. Optionally, additional network connectivity is also provided. A display and / or a user input device (eg, keyboard or mouse) is also optionally further provided.

In the present specification, some embodiments of the present invention are merely exemplified and described with reference to the accompanying drawings. In particular, with reference to the drawings in detail, it is emphasized that the details shown are merely intended to exemplify and consider embodiments of the invention by way of example. In this regard, those skilled in the art will appreciate how to implement the embodiments of the present invention by the description given in the drawings.

FIG. 1A is a representative, unrestricted schematic of a system suitable for addition manufacturing according to some embodiments of the present invention. FIG. 1B is a representative, unrestricted schematic of a system suitable for addition manufacturing according to some embodiments of the present invention. FIG. 1C is a representative, unrestricted schematic of a system suitable for addition manufacturing according to some embodiments of the present invention. FIG. 1D is a representative, unrestricted schematic of a system suitable for addition manufacturing according to some embodiments of the present invention.

2A-2C is a schematic view of a discharge head according to an embodiment of the present invention.

FIG. 3 is a flowchart of a method suitable for manufacturing an article by addition manufacturing according to an embodiment of a part of the present invention.

FIG. 4 is a schematic view of a region containing the interlaced modeling material.

5A-5D are schematic views of typical, unrestricted examples of structures according to aspects of some embodiments of the invention.

6A-6C are schematic views of an object (FIG. 6A) and a stretching device (FIG. 6B) used in measuring static tear resistance in an O-ring test according to aspects of some embodiments of the invention. Also shown are photographs giving such an exemplary assessment before and after subjecting the sample to elongation stress (right object) and after (left object).

FIG. 7 is a comparative plot showing the effect of various concentrations of hydrophobic acrylic coated fumed silica, silica R7200, on the stress-strain curve of a 3D inkjet printed object made from a rubber material obtained from each formulation. Is shown.

FIG. 8 shows hydrophobic acrylic coated fumed silica, silica R7200, and 10% (hydrophilic) colloidal silica for stress-strain curves of 3D inkjet printed objects made from rubber materials obtained from their respective formulations. A comparative plot showing the effect of various concentrations of (silica nanopowder) is shown.

FIG. 9 shows a water pipe connector (left tube) printed using an exemplary formulation according to some embodiments of the invention, after being fitted into the water pipe for 10 hours, and a silica-free formulation. Shows a water pipe connector (the pipe on the right) printed using an object.

The present invention relates to, in some embodiments thereof, with respect to additive manufacturing (AM), but not particularly limited, with formulations and methods that can be used in additional manufacturing of objects made from rubbery materials in at least a portion thereof.

Prior to elaborating on at least one embodiment of the invention, the invention is described in its application below and / or the components and / or methods exemplified in the drawings and / or examples. It must be understood that the details of the assembly and composition of the are not necessarily limited. The present invention may be in other embodiments, or may be practiced or implemented in various ways.

As mentioned above, in addition manufacturing processes such as 3D (inkprint) printing, in contrast to traditional methods of making elastomeric materials, the cured polymer is made from a suitable curable monomer in one step. It allows control of the chemical and mechanical properties of the rubbery material obtained in the challenge of such a process. Thus, current techniques for additive manufacturing often result in rubbery materials characterized by a slow return rate after deformation and / or a low tear resistance (TR) value, for example when compared to conventional elastomers. Rubbery materials that exhibit high elongation thereby are often characterized by low modulus, low tear resistance, and / or low _Tg and toughness.

The inventor has made various types of submicrons (eg, nano) in the addition production of rubbery materials (eg, 3D inkjet printing), including, for example, fine hydrophilic silica, hydrophobic silica, and functionalized (eg acrylic coated) silica. It has been found that the use of size) silica particles results in a rubbery material with improved mechanical properties. The inventor has shown that such a method can be used to obtain a rubbery material with improved elongation, elastic modulus, and tear resistance at the same time.

As shown in the Examples section below, adding submicron silica particles to a formulation currently practiced in 3D inkjet printing of rubbery materials is an object made from the formulation currently practiced. By comparison, it yields a printed object with a tear resistance that is at least 500 N / m higher, and an elastic modulus that is at least twice as high, with tear resistance under constant elongation from minutes / hours to days without compromise. Substantially improve and further improve other properties such as elongation and tensile strength. Such improved mechanical properties were demonstrated using silica particles in an amount up to 10% by weight of the total weight of the formulation.

Referring to the figures, FIGS. 1A-5D show a schematic diagram of an exemplary system, method, and structure according to some embodiments of the invention. 6A-C show figures and photographs showing a method of measuring tear resistance under constant stretching. FIGS. 7 and 8 show that the addition of an increased amount of acrylic coated silica particles results in an increase in the elastic modulus of the resulting rubbery material. FIG. 9 shows photographs showing improved tear resistance of rubbery materials made from formulations containing silica particles according to some embodiments of the invention after use in water pipes. Table 1-4 in the Examples section below further shows the improved mechanical properties of the rubbery material obtained by 3D inkjet printing of the formulation containing silica particles.

Throughout the specification, the terms "rubber", "rubber material", "elastomer material" and "elastomer" are interchangeably used to describe materials having the properties of an elastomer. The term "rubbery material" is used to describe a material that has the properties of a rubber made by additive manufacturing (eg, 3D inkjet printing) rather than a conventional process involving the sulfurization of a thermoplastic polymer.

The term "rubbery material" is also referred to herein interchangeably with "elastomer material".

Elastomers or rubbers are flexible materials characterized by a low _Tg (eg, below room temperature, preferably below 10 ° C, further below 0 ° C, even below −10 ° C).

The following describes some of the properties that characterize the rubber materials used herein and in the industry.

Shore A hardness, also referred to as shore hardness, or simply hardness, describes the resistance of the material to permanent indentations as defined by the A-type durometer scale. Shore hardness is generally determined according to ASTM D2240.

The modulus of elasticity, also referred to as elastic modulus, Young's modulus, tensile modulus, or "E", opposes the resistance of the material to elastic deformation when a force is applied, or in other words, opposite. Described as the tendency of an object to deform along an axis when a force is applied along the axis. The modulus of elasticity is generally measured by a tensile test (eg according to ASM D624) and is determined by the slope of a line of the stress-strain curve in the elastic deformation region, where the stress is exerted by the force that causes the deformation. Divided by area, strain is the ratio of changes in the length parameter caused by the deformation to the initial value of the length parameter. Stress is proportional to the tensile force on the material and strain is proportional to its length.

Tensile strength describes the resistance of the material to tension, or in other words, its ability to withstand the load to be stretched, and is defined as the maximum stress (Mpa) applied during stretching of the elastomeric composite before its fracture. Tensile strength is typically measured by tensile tests (eg, according to ASTM D624) and is determined as the highest point of the stress-strain curve as described herein and in the industry.

伸びは、一般的にＡＳＴＭ Ｄ４１２に従って決定される。 Elongation is the elongation of a uniform cross section of a material, expressed as a percentage of the initial length as follows:

Elongation is generally determined according to ASTM D412.

Z tensile elongation is the elongation measured as described herein when printing in the Z direction.

Tear resistance (TR), also referred to herein and in the industry as "tear strength," describes the maximum force required to tear a material, expressed in N / mm, where this maximum force is the sample. It acts substantially parallel to the main axis of. Tear resistance can be measured by the ASTM D412 method. ASTM D624 can be used to measure resistance to tear formation (tear initiation) and resistance to tear expansion (tear transmission). Generally, the sample is held between the two holders and a uniform tensile force is applied until deformation occurs. Tear resistance is then calculated by dividing the applied force by the thickness of the material. Materials with low tear resistance tend to have poor resistance to wear.

Tear resistance under constant elongation describes the time required for the specimen to be torn when subjected to constant elongation (lower than breaking elongation). This value is determined, for example, in a portion of an example below and in an "O-ring" test as described in FIGS. 6A-C.

Embodiments of the present invention are formulations that can be used to supplementally manufacture three-dimensional (3D) objects or parts thereof made from rubbery materials, supplementary manufacturing processes using them, and processes thereof. Regarding the objects manufactured in.

Throughout the specification, the term "object" refers to the final product of additive manufacturing. The term refers to the product obtained by a method as described herein after removal of the support material, if the support material was used as part of the construction material. The "object" is therefore essentially made of hardened modeling material (consisting of at least 95% by weight).

As used herein throughout, the term "object" refers to an entire article or part of an article.

The object according to the present embodiment is such that at least a part thereof or a part thereof is made of a rubber-like material, and is also referred to in the present specification as an "object made of a rubber-like material". The object can be such that the plurality of parts or parts thereof are made of a rubber-like material, or are completely made of a rubber-like material. The rubbery material can be the same or different in different parts or parts, and for each part, part, or whole object made from the rubbery material, the rubbery material is the same or in the part, part or object. Can be different. When different rubbery materials are used, they can differ in their chemical composition and / or mechanical properties, as further described below.

Throughout the specification, the expressions "construction material formulation", "uncured construction material", "uncured construction material formulation", "construction material", and other variants are therefore collectively referred to herein. Describe the material to be ejected to form the layers continuously, as described in the book. This expression refers to an object, i.e. an uncured material ejected to form one or more uncured modeling material formulations, and a support, i.e., an uncured material ejected to form an uncured supporting material formulation. Includes hardened materials.

Throughout the specification, the expressions "hardened modeling material" and the expression "solidified modeling material" (which are used interchangeably) are referred to as the present when the discharged building material is exposed to curing. As defined herein, the part of the building material that forms the object, as described herein, the part of the building material after removing the cured support material (if any). Represents. The cured modeling material may be a single type of cured material or two or more types of curing, depending on the modeling material formulation used in the method, as described herein. It can be a mixture of the same materials.

The expression "cured (cured) modeling material" or "cured (cured) modeling material compounding" can be regarded as a cured building material consisting only of the modeling material compound (not the supporting material compound) as the building material. can. That is, this representation refers to a portion of the building material, which is used to give the final object.

Throughout the specification herein, the expression "modeling material compounding" (which is also interchangeably, as "modeling compounding", "modeling compounding", "modeling material compounding", or simply "compounding". Shown) describes some or all of the constructs that are ejected to form an object, as described herein. The modeling material formulation is an uncured modeling formulation (unless otherwise indicated), which forms an object or part thereof when exposed to curing energy.

In some embodiments of the invention, the modeling material formulation is formulated for use in 3D inkjet printing and is tertiary on its own, i.e. without the need to be mixed or combined with any other substance. The original object can be formed.

The uncured building material can include one or more shaping formulations, and when cured, different parts of the object are made from different cured shaping formulations or different combinations thereof and thus different. It can be dispensed to be made from a different mixture of cured modeling material or cured modeling material.

The formulations forming the building materials (modeling material formulations and supporting material formulations) include one or more curable materials, which form a solidified (cured) material when exposed to curing energy.

Throughout the specification, a "curable material" is a compound (generally a monomer or oligomer compound) that solidifies or solidifies to form a cured material when exposed to curing energy as described herein. , But optionally a polymer compound). Curable materials are generally polymerizable materials that undergo polymerization and / or cross-linking when exposed to suitable energy sources.

Curable materials according to this embodiment also include materials that solidify or solidify (cure) when exposed to curing conditions (eg, chemical reagents) or simply to the environment, rather than exposed to curing energy.

The terms "curable (curable)" and "coagulable (coagulable)" as used herein are used interchangeably.

The polymerization can be, for example, free radical polymerization, cationic polymerization, or anionic polymerization, each of which can be induced by exposure to curing energies such as radiation, heat, etc., as described herein. ..

In some of the embodiments described herein, the curable material is a photopolymerizable material, which, as described herein, polymerizes or polymerizes when exposed to radiation. And / or crosslinked, in some embodiments the curable material is a UV curable material, which, as described herein, polymerizes or polymerizes when exposed to UV radiation. And / or are subject to cross-linking.

In some embodiments, the curable material as described herein is a photopolymerizable material that polymerizes via photo-induced free radical polymerization. Alternatively, the curable material is a photopolymerizable material that polymerizes by photo-induced cationic polymerization.

In some of the embodiments described herein, the curable material can be a monomer, oligomer, or short chain polymer, each of which can be polymerized as described herein. And / or crosslinkable.

In any part of the embodiments described herein, when the curable material is exposed to curing energy (eg, radiation), it is solidified by any one or a combination of chain extension and cross-linking (eg, radiation). Curing).

In any part of the embodiments described herein, the curable material is a monomer or a mixture of monomers capable of forming the polymerizable material in the polymerization reaction when exposed to the curing energy at which the polymerization reaction takes place. .. Such curable materials are also referred to herein as monomer curable materials.

In some of the embodiments described herein, the curable material is an oligomer or mixture of oligomers that, when exposed to the curing energy at which the polymerization reaction takes place, can form the polymerization material in the polymerization reaction. .. Such curable materials are also referred to herein as oligomeric curable materials.

In any part of the embodiments described herein, the curable material may be a monofunctional curable material or a polyfunctional curable material, whether it is a monomer or an oligomer. can.

As used herein, a monofunctional curable material comprises one functional group that can undergo polymerization when exposed to curing energy (eg, radiation).

Polyfunctional curable materials include two or more, eg, two, three, four or more functional groups that can undergo polymerization when exposed to curing energy. Polyfunctional curable materials can be, for example, bifunctional, trifunctional, or tetrafunctional curable materials, each containing two, three or four groups capable of undergoing polymerization. Two or more functional groups in a polyfunctional curable material are bonded together by a bonding moiety, as is generally defined herein. When the binding moiety is an oligomer or polymer moiety, the polyfunctional group is an oligomer or polymer polyfunctional curable material. The polyfunctional curable material can undergo polymerization when subjected to curing energy and / or can act as a cross-linking agent.

As described herein, the method of the present embodiment manufactures a three-dimensional object in a layered manner by forming a plurality of layers with a configuration pattern corresponding to the shape of the object.

The final 3D object is made from a modeling material, or a combination of modeling materials, or a combination of modeling materials and supporting materials or their variants (eg, after curing). All these operations are well known to experts in solid free shape fabrication.

According to some embodiments of the present invention, there is provided a method of additional manufacturing of a three-dimensional object made of an elastomeric (rubbery) material, as described herein.

The method is generally carried out by sequentially forming a plurality of layers in a configuration pattern corresponding to the shape of the object, and thus at least two or three of the layers, as described in more detail below. Each formation of one layer or each formation of the layers discharges a construction material (uncured) containing one or more modeling material formulations, exposing the discharged modeling material to curing energy and thereby curing. Includes forming the shaped material that has been made.

According to an embodiment of the present invention, one or more modeling material formulations include an elastomeric curable material and silica particles. Elastomer curable materials and silica particles can be in the same modeling material formulation, or when more than one modeling material formulation is used, they can be in different modeling material formulations. ..

In some exemplary embodiments of the invention, the object is a construction material comprising two or more different modeling material formulations, each of which is from a different ejection head of an inkjet printing device. Manufactured by discharging (uncured). The modeling material formulation is optionally and preferably deposited in layers during the same passage of the printhead. The combination of modeling material formulations and / or formulations within the layer is selected according to the desired properties of the object, as described in more detail below.

As used herein and in the industry, the expression "digital material" is a microscopic scale such that the printed area of a particular material is at the level of a few voxels or at the level of one voxel. Alternatively, describe a combination of two or more materials at the voxel level. Such digital materials can exhibit new properties that are influenced by the type of material and / or the ratio of two or more materials and the choice of relative spatial distribution.

In the exemplary digital material, the modeling material for each voxel or voxel block obtained by curing is independent of the modeling material for adjacent voxels or voxel blocks obtained by curing, and thus each voxel or voxel. The blocks result in different modeling materials, and the new properties of the whole part are the result of spatial combinations at the voxel level of multiple different modeling materials.

Throughout the specification, whenever the expression "at the voxel level" is used in the context of different materials and / or properties, differences between voxel blocks, as well as multiple voxels or groups of a few voxels. It is meant to include the difference between. In a preferred embodiment, the properties of the whole part are the result of spatial combinations at the voxel block level of a plurality of different modeling materials.

Modeling material compounding and compounding system:
Elastomer curable material:
One or more modeling material formulations that can be used in the methods as described herein include elastomeric curable materials.

The expression "elastomer curable material" describes a curable material as defined herein, which, when exposed to curing energy, provides a cured material with the properties of an elastomer (rubber, or rubbery material). do.

Elastomer curable materials are generally one or more polymerizable (curable) materials that undergo polymerization when exposed to suitable curing energies, which are contacted to the parts that give elasticity to the polymerized and / or crosslinked material. ) Includes groups. Such moieties are alkyl, alkylene chains, hydrocarbons, alkylene glycol groups or chains (eg, oligos or poly (alkylene glycols)), as defined herein, as defined herein. , Urethane, oligourethane, or polyurethane moieties, and similarities, as well as any of the combinations described above, referred to herein as "elastomer moieties."

式中、Ｒ_１及びＲ_２の少なくとも一つは、本明細書に規定されるようなエラストマー部分であるか、及び／又はそれを含む。 The elastomeric monofunctional curable material according to some embodiments of the present invention can be a vinyl-containing compound represented by Formula I:

In the formula, at least one of R ₁ and R ₂ is and / or includes an elastomeric moiety as defined herein.

The = CH ₂ group in Formula I represents a polymerizable group and, according to some embodiments, is a UV curable group, thus the elastomeric curable material is a UV curable material.

For example, R ₁ is or contains an elastomeric moiety as defined herein, and R ₂ is, for example, hydrogen, C, unless it interacts with the elastomeric properties of the cured material. (1-4) Alkyl, C (1-4) alkoxy, or any other substituent.

In some embodiments, R ₁ is a carboxylate and the compound is a monofunctional acrylate monomer. In some of these embodiments, R ₂ is methyl and the compound is a monofunctional methacrylate monomer. Curable materials in which R ₁ is carboxylate and R ₂ is hydrogen or methyl are collectively referred to herein as "(meth) acrylates".

In some of these embodiments, the carboxylate group —C (= O) —OR _a comprises an elastomer moiety, _Ra , as described herein.

In some embodiments, R ₁ is an amide and the compound is a monofunctional acrylamide monomer. In some of these embodiments, R ₂ is methyl and the compound is a monofunctional methacrylamide monomer. Curable materials in which R ₁ is an amide and R ₂ is hydrogen or methyl are collectively referred to herein as "(meth) acrylamide".

(Meta) acrylates and (meth) acrylamides are collectively referred to herein as (meth) acrylic materials.

In some embodiments, R ₁ is a cyclic amide, in some embodiments it is a cyclic amide such as lactam, and the compound is vinyl lactam. In some embodiments, R ₁ is a cyclic carboxylate, such as a lactone, and the compound is a vinyl lactone.

When one or both of R ₁ and R ₂ contain a polymer or oligomer moiety, the monofunctional curable material of formula I is an exemplary polymer or oligomer monofunctional curable material. Otherwise, it is an exemplary monomeric monofunctional curable material.

In polyfunctional elastomeric materials, two or more polymerizable groups are linked together by an elastomeric moiety as described herein.

In some embodiments, the polyfunctional elastomeric material can be represented by Formula I as described herein, where _R1 is a polymerizable group as described herein. Includes elastomeric materials ending in.

式中、Ｅは、本明細書に記載されるようなエラストマー結合部分であり、Ｒ’_２は、Ｒ_２に対して本明細書に規定されたようなものである。 For example, a bifunctional elastomer curable material can be represented by the following formula I ^* :

In the formula, E is an elastomeric binding moiety as described herein and _R'2 is as defined herein for _R2 .

式中、Ｅは、本明細書に記載されるようなエラストマー結合部分であり、Ｒ’_２及びＲ”_２は、各々独立して、Ｒ_２に対して本明細書に規定されたようなものである。 In another example, the trifunctional elastomer curable material can be represented by Formula II:

In the formula, E is an elastomeric binding moiety as described herein, and _R'2 and R " ₂ are each independently as defined herein for R ₂ . Is.

式中、Ｒ_２及びＲ’_２は、本明細書に規定されるようなものであり、
Ｂは、（Ｘ_１の性質に依存して）本明細書に規定されるような二官能又は三官能枝分かれ単位であり、
Ｘ_２及びＸ_３は、各々独立して、存在しないか、本明細書に記載されるようなエラストマー部分であるか、又はアルキル、炭化水素、アルキレン鎖、シクロアルキル、アリール、アルキレングリコール、ウレタン部分、及びそれらのいずれかの組み合わせから選択され、
Ｘ_１は、存在しないか、又はアルキル、炭化水素、アルキレン鎖、シクロアルキル、アリール、アルキレングリコール、ウレタン部分、及びエラストマー部分（各々は、任意選択的にメタ（アクリレート）部分（Ｏ－Ｃ（＝Ｏ）ＣＲ”_２＝ＣＨ_２）によって置換（例えば終了）される）、及びそれらのいずれかの組み合わせから選択され、又はＸ_１は、以下のものである：

式中、曲線は、結合点を表わし、
Ｂ’は、枝分かれ単位であり、それは、Ｂと同じであるか又はＢとは異なり、
Ｘ’_２及びＸ’_３は、各々独立して、Ｘ_２及びＸ_３に対して本明細書に規定されるようなものであり、
Ｒ”_２及びＲ”’_２は、Ｒ_２及びＲ’_２に対して本明細書に規定されるようなものであり、
但し、Ｘ_１、Ｘ_２、及びＸ_３の少なくとも一つは、本明細書に記載されるようなエラストマー部分であるか、又はそれを含む。 In some embodiments, the polyfunctional (eg, bifunctional, trifunctional, or more functional) elastomeric curable material can be collectively represented by Formula III:

In the formula, R ₂ and _R'2 are as defined herein.
B is a bifunctional or trifunctional branching unit as defined herein (depending _on the nature of X1).
X ₂ and X ₃ are each independently absent, are elastomeric moieties as described herein, or are alkyl, hydrocarbon, alkylene chain, cycloalkyl, aryl, alkylene glycol, urethane moieties. , And any combination of them,
X ₁ is absent or has an alkyl, hydrocarbon, alkylene chain, cycloalkyl, aryl, alkylene glycol, urethane moiety, and elastomer moiety (each optionally optionally a meta (acrylate) moiety (OC (=). O) replaced (eg, terminated) by CR " ₂ = CH ₂ ), and selected from any combination thereof, or X ₁ is:

In the formula, the curve represents the connection point and
B'is a branching unit, which is the same as or different from B,
_X'2 and _X'3 , respectively, are as defined herein for X2 and X3 _{, respectively} .
R " ₂ and R"' ₂ are as defined herein for _R2 and _R'2 .
However, at least one of X ₁ , X ₂ and X ₃ is or includes an elastomeric moiety as described herein.

The term "branching unit" as used herein describes multiple radicals, preferably aliphatic or alicyclic groups. By "plurality of radicals" it is meant that the bonding moiety has more than one bonding point and thus it is bonded between two or more atoms and / or groups or moieties.

That is, when a branching unit is attached to a single position, group, or atom of a substance, it forms two or more functional groups that are attached to this single position, group, or atom, and thus a single. It is the chemical part that "branches" a sensuality into two or more sensualities.

In some embodiments, the branching unit is derived from a chemical moiety having two, three, or more functional groups. In some embodiments, the branching unit is a branched alkyl or branched binding moiety as described herein.

Polyfunctional elastomer curable materials with four or more polymerizable groups are also conceivable and may contain a structure similar to that given in Formula III (provided, eg, include a branching unit B with a larger branching, or Including the X1 moiety with _two (meth) acrylate moieties as defined herein), or a structure similar to that given in Formula II (provided, for example, another bonded to an elastomeric moiety. (Including a (meth) acrylate moiety) can be provided.

In some embodiments, the elastomeric moiety (eg, the moiety represented as _Ra in Formula I or E in Formulas I ^* , II and III) is or contains an alkyl, which is linear. Or can be branched, it is preferably 3 or more or 4 or more carbon atoms; preferably 3 or more or 4 or more lengths of carbon. Atomic alkylene chain; alkylene glycol, oligo (alkylene glycol) as specified herein, or poly (alkylene glycol) as specified herein with a length of four or more atoms. ), Preferably urethane, oligourethane, or polyurethane, or a combination thereof, as defined herein with a length of four or more carbon atoms.

In some of the embodiments described herein, the elastomeric curable material is a (meth) acrylic curable material as described herein, and in some embodiments it is. , Acrylic.

In some of the embodiments described herein, the elastomeric curable material is or comprises a monofunctional elastomer curable material, and in some embodiments, the monofunctional elastomer curable material. Is expressed by the formula I, in which R ₁ is —C (= O) —OR _a , where R _a is an alkylene chain (eg, 4 or more, as defined herein). More, preferably 6 or more, preferably 8 or more carbon atom lengths), or poly (alkylene glycol) chains.

In some embodiments, the elastomeric curable material is or comprises a polyfunctional elastomer curable material, and in some embodiments, the polyfunctional elastomer curable material is represented by Formula I ^* . In the formula, E is an alkylene chain (eg, length of 4 or more, or 6 or more carbon atoms) and / or a poly (alkylene glycol) chain, as defined herein. Is.

In some embodiments, the elastomeric curable material is or comprises a polyfunctional elastomer curable material, and in some embodiments, the polyfunctional elastomer curable material is represented by Formula II, of formula II. Medium, E is a branched alkyl (eg, 3 or more, 4 or more, or 5 or more carbon atom lengths).

In some of the embodiments described herein, the elastomeric curable material is, for example, an elastomer acrylate or methacrylate of formula I, I ^* , II or III (also referred to as acrylic or methacrylic elastomer). Yes, in some embodiments, the acrylate or methacrylate is selected such that the polymer material comprises a _Tg below 0 ° C or below -10 ° C when cured.

Exemplary elastomer acrylates and methacrylate curable materials include 2-propanoic acid, 2-[[(butylamino) carbonyl] oxy] ethyl ester (exemplary urethane acrylate), and trade names SR335 (lauryl acrylate) and SR395 ( Isodecyl Acrylate), including, but not limited to, compounds sold under (by Sartomer). Other examples include trade names SR350D (trifunctional trimethylolpropane trimethacrylate (TMPTMA)), SR256 (2- (2-ethoxyethoxy) ethyl acrylate), SR252 (polyethylene glycol (600) dimethacrylate), SR561 (arcocyclylation). Includes compounds sold under (hexanediol diacrylate) (by Sartomer).

It should be noted that other acrylic materials having one or more acrylamide groups instead of, for example, one or more acrylates or methacrylate groups are also considered.

In some of the embodiments described herein, one or more elastomeric curable materials are included in one or more modeling material formulations, as described in more detail below.

In some of the embodiments described herein, the elastomeric curable material is, in any one of the embodiments as described herein, one or more monofunctional elastomer curable materials ( Includes, for example, monofunctional elastomer acrylates as represented by formula I) and one or more polyfunctional (eg, bifunctional) elastomer curable materials (eg, bifunctional elastomer acrylates as represented by formula I ^* , II, or III). ..

In any part of the embodiments described herein, the total amount of the elastomeric curable material is at least 40%, or at least 50%, or at least the total amount of the modeling material formulation or the formulation containing it. It is 60% and can be up to 70%, or even up to 80%.

In some embodiments, one or more modeling material formulations include a type of modeling material formulation. In some embodiments, one or more modeling material formulations include two or more formulations, and one or more elastomeric curable materials are included within one, two, or all types of formulations. ..

Throughout the specification, one or more modeling material formulations are also referred to herein as compounding systems, as described in more detail below.

Silica particles:
Each of one or more modeling formulations comprises at least one curable material, and at least one of the modeling formulations contains silica particles.

In some of the embodiments described herein, the silica particles have an average particle size less than 1 micron, i.e. the silica particles are submicron particles. In some embodiments, the silica particles have an average particle size in the range of 0.1 nm to 900 nm, or 0.1 nm to 700 nm, or 1 nm to 700 nm, or 1 nm to 500 nm, or 1 nm to 200 nm, and between them. Includes any intermediate and lower range of.

In some embodiments, at least some of such particles can aggregate when introduced into the formulation. In some of these embodiments, the aggregates have an average size of 3 microns or less, or 1.5 microns or less.

Commercially available formulations of any of the submicron silica particles are available in the context of this embodiment, they are fumed silica, colloidal silica, precipitated silica, layered silica (eg montmorillonite), and. Includes aerosol-assisted self-assembly of silica particles.

Silica particles can be such that they have a hydrophobic or hydrophilic surface. The hydrophobicity or hydrophilicity of the surface of a particle is determined by the nature of the surface groups on the particle.

When the silica is untreated, that is, substantially composed of Si and O atoms, the particles generally have silanol (Si—OH) surface groups and are therefore hydrophilic. Untreated (uncoated) colloidal silica, fumed silica, precipitated silica, and layered silica all have a hydrophilic surface and are considered to be hydrophilic silica.

Layered silica can be treated to comprise quaternary ammonium and / or long chain hydrocarbons ending with ammonium as surface groups, the surface properties of which are determined by the length of the hydrocarbon chain. Hydrophobic silica is the form of silica in which hydrophobic groups are attached to the surface of the particles and is also referred to as treated silica or functionalized silica (silica reacted with hydrophobic groups).

As defined herein, moderate lengths of alkyl, preferably two or more carbon atoms, preferably four or more, or six or more carbon atoms. Silica particles with unrestricted hydrophobic surface groups such as to a large degree of alkyl, cycloalkyl, aryl, and other hydrocarbons, or hydrophobic polymers (eg, polydimethylsiloxane) are hydrophobic silica particles. ..

Silica particles as described herein can therefore be untreated (non-functional) and are therefore hydrophilic particles.

Alternatively, silica particles as described herein can be treated (functionalized) by reacting to form bonds with portions on their surface.

When the moiety is a hydrophilic moiety, the functionalized silica particles are hydrophilic.

Silica particles with unrestricted hydrophilic surface groups such as hydroxy, amine, ammonium, carboxy, silanol, oxo, and analogs are hydrophilic silica particles.

Functionalized silica particles are hydrophobic when the moiety is a hydrophobic moiety as described herein.

In some of the embodiments described herein, at least some or all of the silica particles have a hydrophilic surface (ie, hydrophilic surface particles of untreated silica, such as colloidal silica, for example. Is).

In some of the embodiments described herein, at least some or all of the silica particles have a hydrophobic surface (ie, hydrophobic silica particles).

In some embodiments, the hydrophobic silica particles are functionalized silica particles, ie silica particles treated with one or more hydrophobic moieties.

In some of the embodiments described herein, at least some or all of the silica particles are hydrophobic silica particles functionalized with curable functional groups (having curable groups on the surface). Particles).

The curable functional group can be any polymerizable group as described herein. In some embodiments, the curable functional group is polymerizable by the same polymerization reaction as the curable monomer in the formulation and / or when exposed to the same curing conditions as the curable monomer. In some embodiments, the curable group is a (meth) acrylic (acrylic or methacrylic) group, as defined herein.

Hydrophilic and hydrophobic, functionalized and untreated silica particles as described herein can be commercially available materials or using industry well known methods. Can be manufactured.

As used in the context of these embodiments, "at least a portion" is at least 10%, or at least 20%, or at least 30%, or at least 40%, or at least 50%, or at least 60%, or at least of the particles. It means 70%, or at least 80%, or at least 90%, or at least 95%, or at least 98%.

The silica particles can also be a mixture of two or more types of silica particles, eg, a mixture of two or more types of any of the silica particles described herein.

In some of the embodiments described herein, the amount of silica particles in the modeling material formulation is from about 1% to about 20% by weight, or about 20% by weight, of the total weight of the modeling material formulation. It ranges from about 1% by weight to about 15% by weight, or from about 1% by weight to about 10% by weight.

In some of the embodiments described herein, the amount of silica particles in the formulation as described herein is from about 1% to about 20% by weight of the total weight of the formulation. %, Or from about 1% to about 15% by weight, or from about 1% to about 10% by weight.

In some embodiments, the compounding system comprises a type of compounding. In some embodiments, the compounding system comprises two or more formulations and the silica particles are contained within one, two, or all formulations.

The amount of silica particles can be manipulated as desired to control the mechanical properties of the cured modeling material and / or the object or portion within it. For example, increasing the amount of silica particles can increase the elastic modulus of the cured modeling material and / or the object or portion thereof containing it.

In some of the embodiments described herein, the amount of silica particles is such that the weight ratio of the elastomeric curable material to the silica particles in one or more modeling material formulations is from about 50: 1 to about. It is as if it were in the range of 4: 1 or about 30: 1 to about 4: 1, or about 20: 1 to about 2: 1 (including any intermediate and subrange between them).

Additional ingredients:
In some of the embodiments described herein, one or more modeling material formulations further include one or more additional curable materials.

The additional curable material can be a monofunctional curable material, a polyfunctional curable material, or a mixture thereof, and each material can be a monomer, an oligomer, or a polymer, or a combination thereof.

Preferably, although not required, the additional curable material can be polymerized, for example, when exposed to the same curing energy at which the curable elastomer material can be polymerized when exposed to light irradiation (eg UV irradiation).

In some embodiments, the additional curable material, when cured, comprises a T _g of the polymerized material higher than the T _g of the elastomeric material, eg, a T g higher than 0 ° C, or a higher T _g than 5 ° C. It is like having a T _g , or a T _g higher than 10 ° C.

Throughout the specification, "T _g " indicates the glass transition temperature defined as the position of the maximum value of the E "curve, and E" is the loss modulus of the material as a function of temperature.

Roughly speaking, as the temperature rises within the temperature range including the _Tg temperature, the state of the material, preferably the polymer material, gradually changes from a glass state to a rubber state.

As used herein, the "T _g range" is a temperature range in which the E "value is at least half of (eg, can be less than or equal to) the T _g temperature as defined above.

Without being bound by any particular theory, it is envisioned that the state of the polymer material will gradually change from a glass state to a rubber state within the _Tg range as defined above. As used herein, the term "T _g " refers to any temperature within the T _g range as defined herein.

In some embodiments, the additional curable material is, for example, a non-elastomer curable material having a _Tg and / or modulus different from that representing an elastomeric material when cured.

In some embodiments, the additional curable material is a monofunctional acrylate or methacrylate ((meth) acrylate). Examples include, but are not limited to, isobornyl acrylate (IBOA), isobornyl methacrylate, acryloylmorpholine (ACMO), phenoxyethyl acrylate sold by Sartomer Company (USA) under trade name SR-339, trade name CN131B. Includes urethane acrylate oligomers as sold below, and any other acrylates and methacrylates that can be used in AM methodologies.

In some embodiments, the additional curable material is a polyfunctional acrylate or methacrylate ((meth) acrylate). A non-limiting example of a polyfunctional (meth) acrylate is propoxylated (2) neopentyl glycol diacrylate, ditrimethylolpropane tetraacrylate (DiTMPTTA), sold by Sartomer Company (USA) under the trade name SR-9003. ), Pentaerythritol tetraacrylate (TETTA), and dipentaerythritol pentaacrylate (DiPEP), and aliphatic urethane diacrylates as sold by, for example, Ebecryl 230. Non-limiting examples of polyfunctional (meth) acrylate oligomers are ethoxylated or methoxylated polyethylene glycol diacrylates or dimethacrylates, ethoxylated bisphenol A diacrylates, polyethylene glycol-polyethylene glycol urethane diacrylates, partially acrylicized polyols. Includes an oligomer, a polyester-based urethane diacrylate as sold as CNN91.

Any other curable material, preferably a curable material, comprising T _g as defined herein is considered as an additional curable material.

In some of the embodiments described herein, one or more modeling material formulations further comprise an initiator for initiating the polymerization of the curable material.

Photoinitiators can be used in these embodiments when all curable materials (elastomers and additional ones (if present)) are polymerizable.

Non-limiting examples of suitable photoinitiators are benzophenones (aromatic ketones) such as benzophenone, methylbenzophenone, Michler ketone, and xanthone; 2,4,6-trimethylbenzoyldiphenylphosphine oxide (TMPO), 2,4. Acylphosphine oxide type photoinitiators such as 6-trimethylbenzoylethoxyphenylphosphine oxide (TEPO), and bisacylphosphinoxide (BAPO); benzoins and benzoinalkyl such as benzoin, benzoin methyl ether, and benzoin isopropyl ether. Contains ethers and the like. Examples of photoinitiators are those sold under alpha aminoketone, bisacylphosphine oxide (BAPO), and Irgacure®.

The photoinitiator can be used alone or in combination with the co-initiator. Benzophenone is an example of a photoinitiator that requires a second molecule, such as an amine, to generate free radicals. After absorbing the radiation, the benzophenone reacts with the tertiary amine by hydrogen abstraction to generate an alpha amino radical that initiates the polymerization of the acrylate. An unlimited example of the type of co-initiator is an alkanolamine such as triethylamine, methyldiethanolamine, and triethanolamine.

The concentration of the photoinitiator can be in the range of about 0.1% by weight to about 0.5% by weight, or about 1% by weight to about 5% by weight in the formulations containing it, and between them. Includes any intermediate and subrange.

In some of the embodiments described herein, one or more modeling material formulations are one or more additional non-curable materials, such as one or more colorants, dispersants, surfactants. , Stabilizers, and inhibitors.

Inhibitors are included in the formulation to prevent or slow down polymerization and / or curing prior to exposure to curing conditions. Commonly used inhibitors such as radical initiators are conceivable.

Commonly used surfactants, dispersants, colorants, and stabilizers are conceivable. An exemplary concentration of each component (if any) is from about 0.01% to about 1% by weight, or about 0.01% to about 0.5% by weight, of the total weight of the formulation containing it. , Or in the range of about 0.01% by weight to about 0.1% by weight.

Exemplary Formulations In some of the embodiments described herein, the elastomeric curable material is a UV curable material, and in some embodiments it is an elastomer (meth) acrylate. For example, elastomer acrylate.

In some of the embodiments described herein, an additional curable component is included in the modeling material formulation, and in some embodiments, this component is a UV curable acrylate or methacrylate. Is.

In some of the embodiments described herein, the silica particles are (meth) acrylate-functionalized silica particles.

In any part of the embodiments described herein, one or more modeling material formulations may be one or more monofunctional elastomer acrylates, one or more polyfunctional elastomer acrylates, one or more monofunctional acrylates or Elastomers and one or more polyfunctional acrylates or methacrylates.

In some of these embodiments, one or more modeling material formulations further comprise, for example, one or more photoinitiators of the Irgacure® family.

In some of the embodiments described herein, all curable materials and silica particles are included in a single modeling material formulation. In these embodiments, the modeling material formulation forms a formulation consisting of a type of modeling material formulation.

In some of the embodiments described herein, the (uncured) building material comprises two or more modeling material formulations. In these embodiments, the modeling material formulation forms a formulation containing two or more modeling material formulations.

In some of these embodiments, one type of modeling material formulation (eg, first formulation or portion A) comprises an elastomeric curable material (eg, elastomer acrylate) and another type of modeling material formulation (eg, elastomer acrylate). For example, the second formulation or part B) contains an additional curable material.

Alternatively, the two modeling material formulations include an elastomeric curable material, and one of the formulations further comprises an additional curable material.

Further alternative, each of the two modeling material formulations is elastomeric curable, but the elastomeric material is different in each formulation. For example, one type of formulation comprises a monofunctional elastomer curable material and another type of formulation comprises a polyfunctional elastomeric material. Alternatively, one formulation comprises a mixture of monofunctional to polyfunctional elastomer curable material ratio W, another type of formulation is a mixture of monofunctional to polyfunctional elastomer curable material ratio Q. However, W and Q are different.

Whenever each of the modeling material formulations comprises the elastomeric materials described herein, one or more modeling material formulations may further comprise additional curable material. In an exemplary embodiment, one type of formulation comprises a monofunctional additional material and another type of formulation comprises a polyfunctional additional material. In a further exemplary embodiment, one type of formulation comprises an oligomeric curable material and another type of formulation comprises a monomer curable material.

Any combination of elastomeric curable materials and additional curable materials as described herein is considered for inclusion in two or more modeling material formulations. The composition of the modeling material formulation and the choice of printing mode allow the production of objects with various properties in a controlled manner, as described in more detail below.

In some embodiments, one or more modeling material formulations are selected to provide a rubbery material with a constant Shore A hardness in the ratio of the elastomeric curable material to the additional curable material.

In some embodiments, a series of modeling material formulations or modeling material formulations (eg, consisting of two or more modeling material formulations) is a series of rubbery materials having a series of Shore A hardness values. give.

In some embodiments, silica particles, one or more photoinitiators, and optionally other components are included in one or both modeling material formulations.

In the exemplary modeling material formulation according to any portion of the embodiments described herein, the curable material is (meth) acrylate.

In any of the exemplary modeling material formulations described herein, the concentration of photoinitiator is from about 1% to about 5% by weight, or about 5% by weight, of the total weight of the formulation or formulation containing it. About 2% to about 5% by weight, or about 3% to about 5% by weight, or about 3% to about 4% by weight (eg, 3,3.1,3.2,3.25,3. 3,3.4,3.5,3.6,3.7,3.8,3.85,3.9% by weight, including any intermediate values between them).

In any of the exemplary modeling material formulations described herein, the concentration of inhibitor is 0% to about 2% by weight, or 0% by weight of the total weight% of the formulation or formulation containing it. From% to about 1% by weight, for example 0,0.1,0.2,0.3,0.4,0.5,0.6,0.7,0.8,0.9 or about. 1% by weight, including any intermediate values between them.

In any of the exemplary modeling material formulations described herein, the concentration of surfactant is 0% to about 1% by weight of the total weight% of the formulation or formulation containing it. For example, 0,0.01,0.05,0.1,0.5 or about 1% by weight, including any intermediate values between them.

In any of the exemplary modeling material formulations described herein, the concentration of the dispersant is 0% to about 2% by weight of the total weight% of the formulation or formulation containing it. For example at 0,0.1,0.5,0.7,1,1.2,1.3,1.35,1.4,1.5,1.7,1.8 or about 2% by weight Yes, including any intermediate values between them.

In an exemplary modeling material formulation according to any portion of the embodiments described herein, the total concentration of the elastomeric curable material is from about 30% to about 90% by weight, or about 40% by weight. It ranges from about 90% by weight, or about 40% by weight to about 85% by weight.

"Total Concentration" means, throughout the specification, the total weight in all or in the blending system of (one or more) modeling material formulations as described herein.

In some embodiments, the elastomeric curable material comprises a monofunctional elastomer curable material and a polyfunctional elastomer curable material.

In some embodiments, the total concentration of the monofunctional elastomer curable material ranges from about 20% by weight to about 70% by weight, or about 30% by weight to about 50% by weight, and any intermediate value between them. And subranges are also included. In an exemplary embodiment, the total concentration of the monofunctional elastomer curable material is from about 50% by weight to about 70% by weight, or from about 55% to about 65% by weight, or from about 55% to about 60% by weight ( For example, 58% by weight), including any intermediate and subrange between them. In an exemplary embodiment, the total concentration of the monofunctional elastomer curable material is from about 30% to about 50% by weight, or from about 35% to about 50% by weight, or from about 40% to about 45% by weight ( For example 42% by weight), including any intermediate and subrange between them.

In some embodiments, the total concentration of the polyfunctional elastomer curable material ranges from about 10% by weight to about 30% by weight. In an exemplary embodiment, the total concentration of the polyfunctional elastomer curable material ranges from about 10% by weight to about 20% by weight, or from about 10% to about 15% by weight (eg, 12% by weight). In an exemplary embodiment, the total concentration of the polyfunctional elastomer curable material is from about 10% to about 30% by weight, or from about 10% to about 20% by weight, or from about 15% to about 20% by weight ( For example, it is in the range of 16% by weight).

In an exemplary modeling material formulation according to any portion of the embodiments described herein, the total concentration of additional curable material is from about 10% to about 40% by weight, or about 15% by weight. It ranges from% to about 35% by weight and includes any intermediate and subrange between them.

In some embodiments, the additional curable material comprises a monofunctional curable material.

In some embodiments, the total concentration of the monofunctional curable material ranges from about 15% by weight to about 25% by weight, or about 20% by weight to about 25% by weight (eg, 21% by weight). Includes any intermediate and subrange between. In an exemplary embodiment, the concentration of the monofunctional elastomer curable material ranges from about 20% by weight to about 30% by weight, or about 25% by weight to about 30% by weight (eg, 28% by weight). Includes any intermediate and subrange between.

In an exemplary modeling material formulation or blending system according to any portion of the embodiments described herein, the elastomeric curable material comprises a monofunctional elastomer curable material and a polyfunctional elastomer curable material. The total concentration of the monofunctional elastomer curable material is from about 30% to about 50% by weight (eg, about 40% to about 45% by weight), or from about 50% to about 70% by weight (eg, about 55% by weight). ~ About 60% by weight), the total concentration of the polyfunctional elastomer curable material is in the range of about 10% by weight to about 20% by weight, and one or more formulations are from about 20% by weight to about 30% by weight. Additional monofunctional curable material is further included at full concentrations in the weight% range.

According to any part of the embodiments described herein, one or more modeling formulations are at least one elastomer monofunctional curable material, at least one elastomer polyfunctional curable material, and at least one elastomer polyfunctional curable material. Includes a type of additional monofunctional curable material.

According to some of the embodiments described herein, the total concentration of the curable monofunctional material ranges from 10% to 30% by weight of the total weight of one or more modeling formulations. be.

According to some of the embodiments described herein, the total concentration of the elastomer monofunctional curable material ranges from 50% to 70% by weight of the total weight of one or more modeling formulations. Is.

According to some of the embodiments described herein, the total concentration of the elastomeric polyfunctional curable material ranges from 10% to 20% by weight of the total weight of one or more modeling formulations. Is.

According to some of the embodiments described herein, the total concentration of the curable monofunctional material ranges from 10% to 30% by weight of the total weight of one or more modeling material formulations. The total concentration of the elastomer monofunctional curable material is in the range of 50% by weight to 70% by weight of the total weight of one or more modeling material formulations, and the total concentration of the elastomer polyfunctional curable material is one kind. It is in the range of 10% by weight to 20% by weight of the total weight of the above-mentioned molding material compound.

According to some of the embodiments described herein, the total concentration of the curable monofunctional material ranges from 20% to 30% by weight of the total weight of one or more modeling material formulations. Is.

According to some of the embodiments described herein, the total concentration of the elastomer monofunctional curable material is 30% to 50% by weight of the total weight of one or more modeling material formulations. It is a range.

According to some of the embodiments described herein, the total concentration of the elastomer monofunctional curable material is 10% to 30% by weight of the total weight of one or more modeling material formulations. It is a range.

According to any portion of the embodiments described herein, the total concentration of the curable monofunctional material ranges from 20% to 30% by weight of the total weight of one or more modeling material formulations. The total concentration of the elastomer monofunctional curable material is in the range of 30% by weight to 50% by weight of the total weight of one or more modeling material formulations, and the total concentration of the elastomer polyfunctional curable material is one kind. It is in the range of 10% by weight to 30% by weight of the total weight of the above-mentioned molding material compound.

In the exemplary modeling material formulations described herein, the concentration of each component is as such when a type of modeling material formulation is used, or in two or more modeling material formulations. Is given as its total concentration when used.

In some embodiments, the modeling material formulation (or two or more modeling material formulations) as described herein is at least 4000 N / m, or at least 4500 N / m, when cured. , Or at least 5000 N / m tear resistance.

In some embodiments, the modeling material formulation (or two or more modeling material formulations) as described herein, when cured, is the same cured form without the silica particles. It is characterized by a tear resistance that is at least 500 N / m, or at least 700 N / m, or at least 800 N / m higher than the tear resistance of the material formulation.

In some embodiments, the modeling material formulation (or more than one modeling material formulation) as described herein is characterized by a tensile strength of at least 2 MPa when cured. ..

In some embodiments, the modeling material formulation (or more than one modeling material formulation) as described herein consists of a cured modeling material and consists of two O-rings and them. It is such that an object comprising a tube connecting the rings of the ring is characterized by tear resistance under constant stretching for at least one hour or at least one day. In some of these embodiments, the object is as depicted in FIGS. 6A-C.

Formulation system and kit:
In any part of the embodiments described herein, the elastomeric curable material as described herein in any one of the respective embodiments, and in any of the respective embodiments, the present specification. Formulation systems containing silica particles as described in the book are provided.

The compounding system may include one type of compounding system or two or more types of compounding system.

In some embodiments, the compounding system is available or for use in additional manufacturing as described herein in any of the respective embodiments, eg, as a modeling material compounding system. ..

The one or more formulations constituting the formulation system of the present embodiment are described in the present specification for one or more modeling material formulations as any combination thereof in any one of the respective embodiments. Each one.

According to any portion of the embodiments described herein, the amount of silica particles in the formulation is 1% to 20% by weight, or 1% to 15% by weight, of the total weight of the formulation. %, Or 1% by weight to 10% by weight.

According to any part of the embodiments described herein, the weight ratio of the total weight of the elastomeric curable material to the total weight of the silica particles in the formulation ranges from 30: 1 to 4: 1. Is.

According to any portion of the embodiments described herein, the amount of elastomeric curable material in the formulation is at least 40% by weight, or at least 50% by weight, of the total weight of the formulation.

According to any part of the embodiments described herein, the elastomeric curable material is herein for an elastomeric curable material in any one of the respective embodiments and any combination thereof. , A monofunctional elastomer curable monomer, a monofunctional elastomer curable oligomer, a polyfunctional elastomer curable monomer, a polyfunctional elastomer curable oligomer, and any combination thereof.

In some embodiments, the elastomeric curable material is represented by formulas I, I ^* , II and III, as described herein in any of the respective embodiments and any combination thereof. Contains one or more materials selected from the materials.

According to any part of the embodiments described herein, the elastomeric curable material and the silica particles are in the same formulation.

According to some of the embodiments described herein, the compounding system further comprises at least one additional curable material.

According to some of the embodiments described herein, the additional curable material is the present for the additional curable material in any one of the respective embodiments and any combination thereof. As described herein, it is selected from monofunctional curable monomers, monofunctional curable oligomers, polyfunctional curable monomers, polyfunctional curable oligomers, and combinations thereof.

According to some of the embodiments described herein, the elastomeric curable material, silica particles, and additional curable material are in the same formulation.

According to any part of the embodiments described herein, the formulation consists of a type of formulation, and according to some embodiments, this formulation is any of the respective embodiments. As described herein, it includes elastomeric curable materials, silica particles, and additional curable materials.

According to any part of the embodiments described herein, the compounding system comprises two or more formulations.

According to some of the embodiments described herein, the compounding system comprises two or more formulations, one formulation comprising an elastomeric curable material and another type of formulation. The object contains an additional curable material. Optionally, the formulation of the two or more comprises an elastomeric curable material, silica particles, and optionally additional curable material, which may be any of the respective embodiments and combinations thereof. As described herein for two or more modeling material formulations.

According to some of the embodiments described herein, the compounding system further comprises at least one additional non-curable material.

According to any portion of the embodiments described herein, the non-curable material is for one or more modeling material formulations in any one of the respective embodiments and any combination thereof. As described herein, it is selected from colorants, initiators, dispersants, surfactants, stabilizers, inhibitors, and combinations thereof.

According to some of the embodiments described herein, the compounding system comprises at least one elastomer monofunctional curable material, at least one elastomer polyfunctional curable material, and at least additional monofunctional curable material. Includes sex materials.

According to some of the embodiments described herein, the total concentration of the monofunctional curable material ranges from 10% to 30% by weight of the total weight of the formulation.

According to some of the embodiments described herein, the total concentration of the elastomer monofunctional curable material ranges from 50% to 70% by weight of the total weight of the formulation.

According to some of the embodiments described herein, the total concentration of the elastomeric polyfunctional curable material ranges from 10% to 20% by weight of the total weight of the formulation.

According to some of the embodiments described herein, the total concentration of the monofunctional curable material ranges from 10% to 30% by weight of the total weight of the formulation and is an elastomeric monofunctional material. The total concentration of the curable material ranges from 50% to 70% by weight of the total weight of the formulation, and the total concentration of the elastomer polyfunctional curable material is 10% to 20% by weight of the total weight of the formulation. Is the range of.

According to some of the embodiments described herein, the total concentration of the monofunctional curable material ranges from 20% to 30% by weight of the total weight of the formulation.

According to some of the embodiments described herein, the total concentration of the elastomer monofunctional curable material ranges from 30% to 50% by weight of the total weight of the formulation.

According to some of the embodiments described herein, the total concentration of the elastomeric polyfunctional curable material ranges from 10% to 30% by weight of the total weight of the formulation.

According to some of the embodiments described herein, the total concentration of the monofunctional curable material ranges from 20% to 30% by weight of the total weight of the formulation and is an elastomeric monofunctional material. The total concentration of the curable material ranges from 30% to 50% by weight of the total weight of the formulation, and the total concentration of the elastomer polyfunctional curable material is 10% to 30% by weight of the total weight of the formulation. Is the range of.

According to any part of the embodiments described herein, the elastomeric curable material is a UV curable elastomer material.

According to some of the embodiments described herein, the elastomeric curable material is an acrylic elastomer.

In some embodiments, the compounding system, when cured, is described herein for one or more modeling material formulations in any one of the respective embodiments and any combination thereof. Characterized by its characteristics.

In some of the embodiments described herein, a modeling material formulation or blending system as described herein in any one of the respective embodiments and any combination thereof. A kit containing is provided.

In some embodiments, when the kit comprises two or more modeling material formulations, or a formulation containing two or more formulations, each formulation is individually packaged within the kit.

In an exemplary embodiment, the formulation is contained in a suitable packaging material, preferably in an impermeable material (eg, a material impermeable to water and gas), more preferably in an opaque material. Will be packaged. In some embodiments, the kit further comprises instructions for using the formulation in an additive manufacturing process, preferably in a 3D inkjet printing process as described herein. The kit may further include instructions for using the formulation in a process according to the method described herein.

In some embodiments, the kit comprises a series of formulations as described herein in any of the respective embodiments, wherein each formulation, when cured, is a series of formulations. Specific properties such that the system provides a series of elastomeric materials (eg, a series of Shore A hardness, or a series of tensile strengths, or a series of compounding systems that impart a series of tear resistance) having a range of values for a particular property. Provide an elastomeric material comprising. As described above, the series of formulations may differ from each other depending on the amount and / or type of silica particles. In some embodiments, each formulation is individually packaged within a kit.

system:
A representative, unrestricted example of a system 110 suitable for AM of an object 112 according to some embodiments of the invention is shown in FIG. 1A. The system 110 includes an additional manufacturing apparatus 114 having a discharge unit 16 including a plurality of discharge heads. Each head preferably comprises an array 122 of one or more nozzles, through which the liquid building material 124 is ejected, as shown in FIGS. 2A-C described below.

Preferably, but not essential, the device 114 is a tertiary inkjet printing device, where the ejection head is an inkjet printing head and the (uncured) construction material is ejected by inkjet technology. This is not always the case for certain applications, and the use of 3D printing technology may not be necessary for additive manufacturing equipment. Representative examples of the addition manufacturing apparatus considered according to various exemplary embodiments of the present invention include, but are not limited to, melt deposition modeling equipment and molten material deposition equipment.

Each discharge head is optionally and preferably supplied via a construction material reservoir, which optionally comprises a temperature control unit (eg, a temperature sensor and / or a heating device), and a material level sensor. Can include. To eject the construction material, a voltage signal is applied to the ejection head and selectively deposits droplets of material through the ejection head nozzle, for example as in piezo electronic inkjet printing technology. The ejection speed of each head depends on the number of nozzles, the type of nozzles, and the applied voltage signal rate (frequency). Such discharge heads are known to those skilled in the field of solid free shape fabrication.

Preferably, but not essential, the total number of ejection nozzles or nozzle arrays is left to half of the ejection nozzles to eject the supporting material formulation and half of the ejection nozzles to eject the modeling material formulation. Is selected to be entrusted. That is, the number of nozzles for injecting the modeling material formulation is the same as the number of nozzles for injecting the supporting material formulation. In the representative example of FIG. 1A, four discharge heads 16a, 16b, 16c, and 16d are shown. Each of the heads 16a, 16b, 16c, and 16d has a nozzle array. In this example, the heads 16a and 16b can be designed for the modeling material formulation and the heads 16c and 16d can be designed for the supporting material formulation. Therefore, the head 16a can discharge the first modeling material formulation, the head 16b can discharge the second modeling material formulation, and both the heads 16c and 16d use the supporting material formulation. It can be discharged. In an alternative embodiment, the heads 16c and 16d can be combined with a single head having, for example, two nozzle arrays for ejecting a support material formulation.

However, it should be understood that it is not intended to limit the scope of the invention and that the number of modeling material ejection heads (modeling heads) and the number of supporting material ejection heads (supporting heads) can be different. In general, the number of modeling heads, the number of supporting heads, and the number of nozzles in each head or head array are predetermined between the maximum ejection rate of the supporting material formulation and the maximum ejection rate of the modeling material formulation. Is selected to give the ratio a. The predetermined value of ratio a is preferably selected to ensure that the height of the modeling material is equal to the height of the supporting material in each formed layer. The general value for a is about 0.6 to about 1.5.

For example, for a = 1, the overall ejection rate of the supporting material formulation is substantially the same as the overall ejection rate of the modeling material formulation when all modeling heads and support heads are operated.

In a preferred embodiment, there are M build heads, each with m arrays of p nozzles, and S support heads, each with s arrays of q nozzles, M × m × p = S × s × q. Each of the M × m build array and the S × s support array is manufactured as separate physical units, which can be assembled and disassembled from the group of arrays. In this embodiment, each such array optionally and preferably comprises its own temperature control unit and material level sensor and receives individually controlled voltages for its operation.

The device 114 may further include a curing (solidification) device 324, which includes any device configured to emit light, heat, etc. capable of curing (solidifying) the deposited material. be able to. For example, the curing device 324 can include one or more radiation sources, which may be, for example, an ultraviolet or visible or infrared lamp, or other electromagnetic radiation source, depending on the modeling material used. It can be an electron beam source. In some embodiments of the invention, the curing device 324 serves to cure or solidify the modeling material.

The discharge head and radiation source are preferably mounted on the frame 128, which serves as a working surface and is preferably operated to reciprocate on the tray 360. In some embodiments of the invention, the radiation source is mounted on the frame to follow the discharge head to at least partially cure or solidify the material just deposited by the discharge head. The tray 360 is positioned horizontally. According to common practice, the XYZ Cartesian coordinate system is chosen so that the XY planes are parallel to the tray 360. The tray 360 is preferably configured to move vertically (along the Z direction), generally downward. In various exemplary embodiments of the invention, device 114 further comprises one or more leveling devices, such as rollers 326. The leveling device 326 helps to trim, equalize, and / or establish the thickness of the newly formed layer before forming the continuous layer on top. The leveling device 326 preferably includes a waste collecting device 136 for collecting excess material generated during leveling. The waste collection device 136 can include either a mechanism for delivering material to a waste tank or a waste cartridge.

In use, the ejection head of the unit 16 moves in the scanning direction referred to herein as the X direction and selectively ejects uncured construction material in a predetermined configuration in the process of moving on tray 360. do. Construction materials generally include one or more types of supporting materials and one or more modeling material formulations. After the discharge head of the unit 16 is moved, the modeling material compound discharged by the radiation source 126 is cured. In the reverse movement of the head back to the starting point for the freshly deposited layer, additional ejection of the (uncured) building material can be carried out according to a predetermined configuration. With forward and / or reverse movement of the discharge heads, the layers thus formed can be straightened by the leveling device 326, which is with their forward and / or reverse movement of the discharge heads. It is preferable to follow the course. Once the discharge heads return to their starting point along the X direction, they move to another position along the index direction referred to herein as the Y direction and by reciprocating along the X direction. You can continue to build the same layer. Alternatively, the discharge head can be moved in the Y direction between forward and reverse movements, or after more than one forward and reverse movement. The series of scans performed by the discharge head to complete a single layer is referred to herein as a single scan cycle.

Once the layer is complete, the tray 360 is lowered to a predetermined Z level in the Z direction according to the desired thickness of the subsequently printed layer. The procedure is repeated to form the three-dimensional object 112 in layers.

In another embodiment, the tray 360 can be displaced in the Z direction between forward and reverse movements of the discharge head of the unit 16 within the layer. Such Z displacement can be performed to cause contact between the surface and the leveling device in one direction and prevent contact in the other direction.

The system 110 optionally and preferably includes a construction material supply device 330, which includes a construction material container or cartridge and supplies a plurality of construction materials to the production device 114.

The control unit 152 controls the manufacturing device 114 and optionally and preferably the supply device 330. The control unit 152 generally includes an electronic circuit configured to perform a control operation. The control unit 152 preferably communicates with the data processing apparatus 154, for example, in Standard Instruction Range (STL) format, Stereo Lithology Contour (SLC) format, Virtual Reality Modeling Range (VRM) format Based on computer object data such as CAD configurations represented on computer-readable media in the form of Exchange Format (DXF), Polygon File Format (PLY), or any other format suitable for computer-aided design (CAD). And send digital data about production instructions. Generally, the control unit 152 controls the voltage applied to each discharge head or nozzle array and the temperature of the material in each print head.

Once the manufacturing data is loaded into the control unit 152, it can be operated without user intervention. In some embodiments, the control unit 152 can receive additional input from the operator, for example using the data processing device 154 or using the user interface 116 that communicates with the control unit 152. The user interface 116 can be of any type known in the industry, such as keyboards, touch screens and the like. For example, the control unit 152 can receive, as additional inputs, one or more construction material types and / or attributes that are not limited, such as color, characteristic strain and / or transition temperature, viscosity, electrical characteristics, magnetic characteristics. .. Other attributes and groups of attributes are also conceivable.

Another representative and unrestricted example of a system 10 suitable for AM of an object according to some embodiments of the invention is shown in FIGS. 1BD. 1B-D show a plan view (FIG. 1B), a side view (FIG. 1C), and an isometric view (FIG. 1D) of the system 10.

In this embodiment, the system 10 includes a tray 12 and a plurality of inkjet printheads 16 each having a plurality of separate nozzles. The tray 12 can have the shape of a disk, or it can be annular. Non-round shapes are also conceivable if they can rotate around a vertical axis.

The tray 12 and the head 16 are optionally and preferably mounted to allow relative rotational movement between the tray 12 and the head 16. This is to (i) configure the tray 12 to rotate around the vertical shaft 14 with respect to the head 16, and (ii) configure the head 16 to rotate around the vertical shaft 14 with respect to the tray 12. This can be accomplished by (iii) configuring both the tray 12 and the head 16 to rotate around the vertical axis 14 but at different rotation speeds (eg, rotation in opposite directions). The following embodiments are described with particular emphasis on configuration (i), which is a rotating tray configured such that the tray rotates about a vertical axis 14 with respect to the head 16. It should be understood that configurations (ii) and (iii) are also conceivable. Any one of the embodiments described herein can be adjusted to be applicable to any of the configurations (ii) and (iii), and one of ordinary skill in the art will describe it herein. Given the details provided, you will know how to make such adjustments.

In the following description, the direction parallel to the tray 12 and facing outward from the axis 14 is referred to as the radial direction r, and the direction parallel to the tray 12 and perpendicular to the radial direction r is the azimuth direction in the present specification. Referenced as φ, the direction perpendicular to the tray 12 is referred to herein as the vertical direction Z.

As used herein, the term "radial position" refers to a position above or above the tray 12 at a particular distance from the axis 14. When the term is used in connection with a print head, the term indicates the position of the head at a particular distance from the axis 14. When the term is used in connection with a point on the tray 12, the term corresponds to any point belonging to the location of a point in a circle whose radius is at a particular distance from axis 14 and whose center is axis 14. do.

As used herein, the term "azimuth position" refers to a position above or above the tray 12 at a particular azimuth angle with respect to a predetermined reference point. Thus, the radial position refers to any point that belongs to the location of a point that is a straight line forming a particular azimuth angle with respect to the reference point.

As used herein, the term "vertical position" refers to a position on a plane that intersects the vertical axis 14 at a particular point.

The tray 12 acts as a support structure for three-dimensional printing. The work area on which the object is printed is generally smaller than the entire area of the tray 12, but is not required. In some embodiments of the invention, the working area is annular. The work area is indicated by 26. In some embodiments of the invention, the tray 12 rotates continuously in the same direction throughout the formation of the object, and in some embodiments of the invention, the tray 12 is at least once (at least once during the formation of the object). Invert the direction of rotation (eg in a vibrating manner). The tray 12 can be optionally and preferably removed. The removal of the tray 12 can be for maintenance of the system 10 or, if desired, to replace the tray before printing a new object. In some embodiments of the invention, the system 10 is provided with one or more different exchange trays (eg, exchange tray kits), where the two or more trays are of different types of objects (eg, different weights). , Specified for different operating modes (eg different rotation speeds) and so on. Replacement of the tray 12 can be manual or automatic, if desired. When automatic replacement is used, the system 10 includes a tray replacement device 36 configured to remove the tray 12 from a position under the head 16 and replace it with a replacement tray (not shown). In the representative view of FIG. 1B, the tray changing device 36 is shown as a driving device 38 having a movable arm 40 configured to pull the tray 12, but other types of tray changing devices are also conceivable.

An exemplary embodiment for the printhead 16 is shown in FIG. 2A-2C. These embodiments can be used for any of the AM systems described above, including, but not limited to, system 110 and system 10.

2A-B show a printhead 16 with one (FIG. 2A) and two (FIG. 2B) nozzle arrays 22. The nozzles in the array are preferably aligned linearly along a straight line. In embodiments where the individual printheads have more than one linear nozzle array, the nozzle arrays can optionally and preferably be parallel to each other.

When a system similar to the system 110 is used, all printheads 16 are optionally and preferably oriented along the index direction at positions along the scanning direction that are offset from each other.

When a system similar to the system 10 is used, all printheads 16 are optionally and preferably oriented radially (parallel to the radial direction) at orientation positions that are offset from each other. Therefore, in these embodiments, the nozzle arrays of different printheads are not parallel to each other, but rather are angled to each other. The angle is approximately equal to the azimuth offset between the heads. For example, one head may be radially oriented and located at azimuth position φ1, and _another head may be radially oriented and located at azimuth position _φ2 . In this example, the azimuth offset between the two heads is φ ₁ − φ ₂ , and the angle between the linear nozzle arrays of the two heads is also φ ₁ − φ ₂ .

In some embodiments, two or more printheads can be assembled into blocks of printheads, in which case the printheads of the blocks are generally parallel to each other. A block containing the plurality of inkjet printheads 16a, 16b, 16c is shown in FIG. 2C.

In some embodiments, the system 10 includes a support structure 30 arranged under the head 16 such that the tray 12 is between the support structure 30 and the head 16. The support structure 30 can help prevent or reduce possible vibration of the tray 12 during operation of the inkjet print head 16. In a configuration in which the print head 16 rotates around a shaft 14, the support structure 30 also has a tray 12 between the heads 16 and a tray 12 so that the support structure 30 is always directly below the head 16. ) It is preferable to rotate.

The tray 12 and / or the printhead 16 optionally and preferably moves along a vertical direction Z parallel to the vertical axis 14 so as to vary the vertical distance between the tray 12 and the printhead 16. It is configured as follows. In a configuration in which the vertical distance is changed by moving the tray 12 along the vertical direction, the support structure 30 is preferably moved in the vertical direction together with the tray 12. In a configuration in which the vertical distance is varied by the head 16 along the vertical direction while maintaining the vertical position of the fixed tray 12, the support structure 30 is also maintained in the fixed vertical position.

Vertical movement can be established by the vertical drive 28. Once the layer is complete, the vertical distance between the tray 12 and the head 16 can be increased by predetermined vertical steps according to the desired thickness of the subsequently printed layer (eg, tray 12). Is lowered relative to the head 16). The procedure is repeated to form a three-dimensional object in a layered manner.

The operation of the inkjet printhead 16 and optionally and preferably one or more other components of the system 10 (eg, movement of the tray 12) is controlled by the control device 20. The control device can have an electronic circuit and a non-volatile storage medium readable by the circuit, which, when read by the circuit, causes the circuit to perform a control operation as further detailed below. Memorize program instructions.

The control device 20 can also communicate with the host computer 24, which may be in any other format suitable for, for example, STL, SLC format, VRML, AMF format, DXF, PLY, or CAD. In the form, it sends digital data about production instructions based on computer object data. Object data formats are generally constructed according to the Cartesian coordinate system. In these cases, the computer 24 implements a procedure for changing the coordinates of each slice in the computer object data from the Cartesian coordinate system to the polar coordinate system. The computer 24 optionally and preferably transmits production instructions regarding the transformed coordinate system. Alternatively, the computer 24 transmits a production instruction regarding the original coordinate system given by the computer object data, in which case the transformation of the coordinates is carried out by the circuit of the control device 20.

The transformation of coordinates enables 3D printing on the rotating tray. In conventional 3D printing, the print head reciprocates on a stationary tray along a straight line. In such conventional systems, the print resolution is the same at all points on the tray, provided that the head ejection speed is uniform. Unlike conventional 3D printing, not all nozzles at the head point cover the same distance on the tray 12 at the same time. The transformation of coordinates is optionally and preferably performed to ensure an equal amount of excess material at different radial positions.

Generally, the control device 152 or 20 controls the voltage applied to each component of the system 10 based on the production instructions and based on the stored program instructions as described below.

In general, the control device 152 or 20 has a print head such that droplets of construction material are ejected in layers as the tray 360 or 12 rotates, eg, to print a three-dimensional object onto the tray 360 or 12. 16 is controlled.

The system 10 or 110 optionally and preferably comprises one or more radiation sources 18, which provide curing energy, for example ultraviolet or visible, depending on the modeling material formulation used. Alternatively, it can be an infrared lamp, or another electromagnetic radiation source, or an electron beam source. The radiation source can include any type of radiation emitting device, including light emitting diodes (LEDs), digital light processing (DLP) systems, resistance lamps (but not limited to them), and the like. The radiation source 18 serves to cure or solidify the modeling material. In various embodiments of the present invention, the operation of the radiation source 18 is controlled by the control device 20, which can activate and inactivate the radiation source 18, optionally the radiation source 18. It is also possible to control the amount of radiation generated by.

In some embodiments of the invention, the system 10 further comprises one or more leveling devices 32 that can be manufactured as rollers or blades. The leveling device 32 helps to reinforce the newly formed layer before forming a continuous layer on it. In some embodiments, the leveling device 32 has the shape of a conical roller whose axis of symmetry 34 is tilted relative to the surface of the tray 12 so that the surface is parallel to the surface of the tray. This embodiment is shown in a side view of the system 10 (FIG. 1C).

The conical roller can have the shape of a cone or a conical frustum.

The opening angle of the conical roller is preferably selected so that there is a constant ratio between the radius of the cone at any position along its axis 34 and the distance between that position and the axis 14. .. This embodiment allows the rollers 32 to efficiently flatten the layers. This is because, while the roller is rotating, any point P on the surface of the roller has a linear velocity proportional to (same) the linear velocity of the tray at the point directly below the point P in the vertical direction. .. In some embodiments, the roller has the shape of a conical facet having a height h, a radius _R1 closest to the axis 14, and a radius _R2 farthest from the axis 14. The parameters h, R ₁ and R ₂ satisfy the relationship R ₁ / R ₂ = (R—h) / h, where R is the farthest distance of the roller from the axis 14 (eg, R is the tray). It can be a radius of 12).

The operation of the leveling device 32 is optionally and preferably controlled by the control device 20, which can activate and inactivate the leveling device 32 and optionally selectively in the vertical direction (axis 14). The position can be controlled along (parallel to) and / or along the radial direction (parallel to tray 12), and can be controlled to point towards or away from axis 14.

In some embodiments of the invention, the printhead 16 of the system 10 is configured to reciprocate with respect to the tray along the radial direction r. These embodiments are useful when the length of the nozzle array 22 of the head 16 is shorter than the radial width of the working area 26 on the tray 12. The movement of the head 16 along the radial direction is arbitrarily and preferably controlled by the control device 20.

Further details on the principles and operations of the AM system suitable for this embodiment can be found in US Publication No. Found in 2010011360, its contents are incorporated herein by reference.

Method:
FIG. 3 provides a flowchart illustrating an exemplary method according to an embodiment of the present invention.

Unless otherwise specified, it should be understood that the operations described below can be performed simultaneously or sequentially in many combinations or sequences of implementations. In particular, the order of the flow charts should not be considered as a limitation. For example, two or more operations appearing in a flow chart or in the description below in a particular order can be performed in different orders (eg, in reverse order) or substantially simultaneously. Further, the plurality of operations described below are optional and may not be performed.

Computer programs that implement the methods of this embodiment can generally be distributed to users in an unlimited distribution medium such as floppy disks, CD-ROMs, flash memory devices, and portable hard drives. From the distribution medium, the computer program can be copied to a hard disk or similar intermediate storage medium. Computer programs can be executed by loading computer instructions from their distribution media or their intermediate storage media into a computer's implementation storage device that is configured to operate the computer according to the methods of the invention. All these operations are well known to experts in the field of computer systems.

The computer-implemented method of this embodiment can be realized in many embodiments. For example, it can be realized in a tangible medium of expression such as a computer for performing method operations. It can be implemented in computer-readable media, including computer-readable instructions for performing method operations. It can also be implemented in an electronic device with digital computer capabilities arranged to run a computer program on a tangible medium of expression or to execute instructions on a computer readable medium.

The method starts at 200 and optionally follows 201, where computer object data (eg, 3D print data) corresponding to the shape of the object is received. The data can be received, for example, from the host computer, for example in computer object data, such as STL, SLC format, VRML, AMF format, DXF, PLY, or any other CAD suitable format. Send digital data about production instructions based on the shape.

The method follows 202, wherein an uncured construction material as described herein (eg, one or more modeling material formulations as described herein, and optionally a supporting material formulation). Droplets of objects) follow computer object data (eg, print data) and, as described herein, optionally and optionally an AM system such as system 110 or system 10 (but not limited to these). Preferably used to be dispensed in layers on the receiving medium. In any of the embodiments described herein, the ejection 202 is performed by at least two different multi-nozzle inkjet printheads. The receiving medium can be a tray of the AM system (eg, tray 360 or 12) as described herein, or a previously deposited layer.

In some embodiments of the invention, the discharge 202 is performed in an ambient environment.

Optionally, the uncured construction material, or a portion thereof (eg, one or more formulations of the construction material), is heated before being ejected. These embodiments are particularly useful for uncured construction material formulations that have a relatively high viscosity at the operating temperature of the working room of a 3D inkjet printing system. The heating of the formulations is preferably at a temperature that allows the respective formulations to be ejected through the nozzles of the print head of the 3D inkjet printing system. In some embodiments of the invention, heating is to a temperature at which each formulation exhibits a viscosity of X centipores or less. Here, X is about 30 centipores, preferably about 25 centimeters, more preferably about 20 centimeters or 18 centimeters, or 16 centimeters, or 14 centimeters, or 12 centimeters, or 10 centimeters, or even lower.

Heating is performed before filling the printhead of the AM (eg, 3D inkjet printing) system with each formulation, or while the formulation is in the printhead, or while the composition passes through the nozzles of the printhead. Can be printed.

In some embodiments, heating is applied to each formulation into the ejection (eg, inkjet printing) head to avoid clogging of the ejection (eg, inkjet printing) head by the formulation if the formulation is too viscous. It is carried out before filling.

In some embodiments, heating is performed by heating the ejection (eg, inkjet printing) head at least while the modeling material formulation passes through the nozzles of the ejection (eg, inkjet printing) head.

Once the uncured construction material is ejected onto the receiving medium according to computer object data (eg, print data), the method optionally follows 203, where the curing energy is described, eg, herein. It is applied to the layer deposited by such a radiation source. Preferably, the cure is applied to each individual layer after the layer has been deposited and before the previous layer has been deposited.

In some embodiments, the application of curing energy is carried out in a nearly dry, inert environment, as described herein. The method ends at 204.

In some embodiments, the method is performed using an exemplary system as described herein in any one of the respective embodiments and any combination thereof.

The modeling material formulation can be included in a particular container or cartridge of a solid free-form fabrication device, or a combination of modeling material formulations deposited from different containers of the device.

In some embodiments, at least one, or at least two or three (eg, at least 10, at least 20, at least 30, at least 40, at least 50, at least 60, at least 80, or more), or all. The layer is formed by the ejection of droplets as in 202 of a single modeling material formulation, as described herein in any of the respective embodiments.

In some embodiments, at least one, or at least two or three (eg, at least 10, at least 20, at least 30, at least 40, at least 50, at least 60, at least 80, or more), or all. Layers, such as in 202 of two or more modeling material formulations, each from a different ejection (eg, inkjet printing) head, as described herein in one of the respective embodiments. It is formed by ejecting droplets.

These embodiments specifically provide the ability to select materials from a predetermined number of materials and define the desired combination of selected materials and their properties. According to the present embodiment, the spatial position of the deposition of each material in the layer either implements the occupation of different three-dimensional spatial positions by different materials, or is substantially the same three-dimensional position by two or more different materials. It is defined to carry out occupancy of adjacent three-dimensional positions and allow post-deposit space combinations of materials within the layer, thereby forming composite materials at each position.

Any later deposition combination or mixing of modeling materials is also conceivable. For example, once a material is ejected, it can retain its original properties. However, when it is ejected at the same time as another shaped material or other ejected material ejected at the same or adjacent positions, a composite material with different properties than the ejected material is formed.

Part of the embodiment allows the ejection of a wide range of material combinations and the fabrication of objects consisting of multiple different material combinations according to the desired properties for characterizing each part of the object in different parts of the object. do.

In some of these embodiments, two or more modeling material formulations are ejected in a voxel fashion, and one of the modeling material formulations is a voxel of at least one other type of modeling material. Interlaced with voxels in the formulation.

Some embodiments provide a method of layered fabrication of a three-dimensional object, in which at least two or three (eg, at least 10, at least 20, at least 30, at least 40, or at least 80) layers or all. For each of the layers, two or more modeling material formulations are optionally and preferably dispensed using system 10 or system 110. Each modeling material formulation is preferably ejected by ejecting it from a plurality of nozzles of a print head (eg, head 16). The discharge is performed by a voxel method, and one type of voxel in the modeling material formulation is interlaced with at least one other type of modeling material formulation voxel according to a predetermined voxel ratio.

Such a combination of two modeling material formulations at a predetermined voxel ratio is referred to as a digital material (DM). A representative example of a digital material is shown in FIG. 4, which shows materials A and B interlaced over a region of layers in a voxel fashion.

In some embodiments, ejection of the two modeling material formulations at a predetermined voxel ratio makes it possible to obtain a rubbery material with the desired mechanical properties. For example, by manipulating the voxel ratio, a series of rubbery digital materials with various Shore A hardness values can be obtained in a controllable digital manner.

For any predetermined ratio of material, the digital material can be formed, for example, by ordered or chaotic interlacing. An embodiment in which the interlacing is semi-disordered (for example, a repeating pattern of sub-regions in which each sub-region contains chaotic interlacing) is also conceivable.

In some of the embodiments described herein, droplets of two or more modeling material formulations are ejected in each of at least two or three layers as described herein. When so, the discharge is such as forming a core region and one or more cover regions that at least partially surround the core region. Such ejection results in the production of an object composed of a plurality of layers, a layered core constituting the core region, and a layered sheath constituting the outer cover region.

The structure of some of these embodiments is a sheathed structure made of two or more curable materials. This structure generally includes a layered core that is at least partially covered by one or more layered sheaths such that at least one layer of core engages in the same plane as at least one layer of sheath. The thickness of each sheath measured perpendicular to the surface of the structure is generally at least 10 μm. In various exemplary embodiments, the wicks and sheaths differ from each other in their thermomechanical properties. This is easily achieved by making cores and sheaths from different modeling material formulations or combinations of different modeling material formulations. The thermomechanical properties of the core and sheath are referred to herein as "core thermomechanical properties" and "sheath thermomechanical properties," respectively.

Representative, but not limited to, structural examples according to some embodiments of the invention are shown in FIGS. 5A-D.

5A is a schematic perspective view of the structure 60, and FIG. 5B is a cross-sectional view of the structure 60 along the line AA of FIG. 5A. A Cartesian coordinate system is also shown for clarity of presentation.

The structure 60 includes a plurality of layers 62 stacked along the Z direction. The structure 60 is generally made by AM technology, for example using system 10 or system 110, whereby layers are formed in a continuous manner. Therefore, the Z direction is also referred to herein as the "building direction" of the structure. Therefore, the layer 62 is perpendicular to the construction direction. Structure 60 is shown as a cylinder, but this does not necessarily have to be the case. This is because the structure of this embodiment can have any shape.

The sheath and core of structure 60 are designated by 64 and 66, respectively. As shown, the layer of core 66 and the layer of sheath 64 are coplanar. AM technology allows for the simultaneous fabrication of sheath 64 and core 66, whereby for a particular formed layer, the inner portion of the layer constitutes the core layer, and the perimeter or part thereof of the layer. Consists of a layer of pods.

The area surrounding the layer that contributes to the sheath 64 is referred to herein as the "coating area" of the layer. In the unrestricted examples of FIGS. 5A and 5B, each of the layers 62 has an outer cover region. That is, each layer in FIGS. 5A and 5B contributes to both the core and the sheath. However, this does not necessarily have to be the case. This is because for some applications it may be desirable for the wick to be exposed to the environment in some areas. In these applications, at least a portion of the layer does not include an outer cover area. A representative example of such a configuration is shown in the cross-sectional view of FIG. 5C, which shows that some layers 68 contribute to the core rather than the sheath, and some layers 70 contribute to both the core and the sheath. Has been done. In some embodiments, the one or more layers do not include regions with core thermomechanical properties, only regions with sheath thermomechanical properties. These embodiments are particularly useful when the structure has one or more thin portions, where the layers forming those portions of the structure preferably lack core regions. An embodiment is also conceivable in which one or more layers do not include a region having sheath thermomechanical properties but only a region having core thermomechanical properties.

The sheath can also optionally and preferably cover the structure 60 from above and / or below in the Z direction. In these embodiments, some layers at the top and / or bottom of the structure 60 have at least one material property different from that of the core 66. In various exemplary embodiments of the invention, the top and / or bottom portion of the structure 60 has the same material properties as the sheath 64. A representative example of this embodiment is shown in FIG. 5D. The upper / lower sheath of the structure 60 may be thinner (eg, twice thinner) than the side sheath. This may be the case, for example, when the upper or lower sheath comprises an upper or lower layer of the structure and therefore has the same thickness as required for the layer forming the object.

In some embodiments of the invention, both the core and the sheath are rubbery materials.

In some embodiments of the invention, both the core and the sheath are DM materials.

When both the core and the sheath are made from DM composed of the same modeling material formulation, the relative surface density of any of the modeling materials in the core is the relative surface density of that material in the sheath or sheath area. Is different. However, in some embodiments, the core is formed from DM and the sheath is formed from a single type of modeling material formulation and vice versa.

In various exemplary embodiments of the invention, the sheath thickness measured in the XY plane (perpendicular to the construction direction Z) is non-uniform across the construction direction. In other words, layers with different structures can have outer covering areas of different widths. For example, the thickness of the sheath along a direction parallel to the XY plane can be calculated as a percentage of the diameter of each layer along that direction, thus depending on the size of the layer. Let me. In various exemplary embodiments of the invention, the thickness of the sheath is non-uniform across a direction that is tangent to the outer surface of the sheath and perpendicular to the construction direction. With respect to the layers of the structure, these embodiments correspond to an outer cover area having a non-uniform width along the perimeter of each layer.

In some embodiments of the invention, the sheath of the structure, or part thereof, is a "sheathed" structure that alone comprises the jacket area and the rest. Particularly in these embodiments, the structure comprises an inner core that is at least partially surrounded by at least one intermediate coat region, which is surrounded by an outer coat region. When measured perpendicular to the construction direction, the thickness of the intermediate coat region is optionally greater than the thickness of the outermost cover region (eg, 10 times or more). In these embodiments, the intermediate coat region serves as a sheath for the structure and therefore has the properties of a sheath as further detailed above. The outermost sheath can also help protect the intermediate sheath from fracture under load.

The structure of this embodiment can be formed in a layered manner, as described above, using, for example, the system 10 or 100 described above. In various exemplary embodiments of the invention, computer embodiments automatically implement dynamic adaptation of the sheath to specific elements of the structure. The method can optionally and preferably use user input to calculate sheaths for each region of the structure and assign voxels on the outer surface to each shaping material or combination of shaping materials. .. The computer implementation method can be implemented by a control unit (eg, control unit 152 or 20, see FIGS. 1A and 1B) that controls the solid freeform fabrication device by a data processing device (eg, data processing device 154 or 24).

In some embodiments of the invention, one or more additional sheath layers are ejected to form a sheath at the top and / or bottom of the structure. These layers preferably lack a core region. Because they are useful for removing the wick from above or below. When it is desirable to remove the wick from above, an additional sheath layer is ejected over all other layers, and when it is desirable to remove the wick from below, the additional layer is a working surface (eg, tray 360 or 12, FIG. 1A and 1B) are ejected, while all other layers are subsequently ejected.

Any of the covering regions optionally has a width of at least 10 μm. Preferably, all cover regions have a width of at least 10 μm.

Either the core or the outer cover area, and optionally the top and / or bottom additional layer, may be a modeling material formulation or a combination of modeling material formulations as described herein (eg, digital). Can be manufactured using materials).

In some embodiments of the invention, sheaths are selectively made in regions of different structure such that the mechanical properties change only to a selected region area without affecting the mechanical properties of other regions. To.

In any part of the embodiment of the invention, once the layer is ejected as described herein, exposure to curing energy as described herein is carried out. In some embodiments, the curable material is a UV curable material and the curing energy is such that the radiation source emits UV radiation.

In some embodiments, if the construction material also comprises a support material formulation, the method is performed to remove the support material formulation. This can be done by mechanical and / or chemical means, as recognized by those of skill in the art.

object:
Embodiments of the present invention provide a three-dimensional object containing at least a portion of an elastomeric material.

When an object is made from a single modeling material formulation, as described herein, it is described herein for the modeling material formulation when cured (solidified). It has such mechanical properties.

In some embodiments, the object is made from two or more modeling material formulations, and in some of these embodiments, at least a portion of the object is digital, as described herein. Made from materials. In some embodiments, the object comprises a core-sheath structure as described herein in any one of the respective embodiments, with properties according to the selected material and structure.

In some embodiments, the object is made of different elastomeric materials in different parts (eg, two or more parts), each of which has different properties (eg different Shore A hardness, different modulus) as desired. Etc.).

Many relevant elastomeric curable materials, other curable materials, and silica particles are expected to be developed during the term of the patent that matures from this application, "Elastomer Curable Materials", ". The scope of the terms "curable material" and "silica particles" is intended to include all such new techniques a priori.

As used herein, the term "about" refers to ± 10% or ± 5%.

The terms "compriss, comprising, includes, including", "having", and their cognates mean "include but not limited to". ..

The term "consisting of" means "inclusion and limited to".

The expression "consisting essentially of" is used only if the additional ingredients, processes and / or moieties do not substantially alter the basic and novel features of the claimed composition, method or structure. , The composition, method or structure may include additional components, steps and / or moieties.

As used herein, the singular form ("a", "an" and "the") includes multiple references unless the context explicitly indicates otherwise. For example, the term "a compound" or the term "at least one compound" may include a plurality of compounds, including a mixture thereof.

Through the present disclosure, various aspects of the invention may be presented in a range format. It should be understood that the description in range format is for convenience and brevity only and should not be construed as an inflexible limitation on the scope of the invention. Therefore, the description of a range must be considered to have all possible subranges specifically disclosed, as well as the individual numbers contained within that range. For example, the description of the range such as 1 to 6 includes the specifically disclosed partial range (for example, 1 to 3, 1 to 4, 1 to 5, 2 to 4, 2 to 6, 3 to 6 and the like), and , Must be considered to have individual numerical values within that range (eg, 1, 2, 3, 4, 5 and 6). This applies regardless of the breadth of the range.

Whenever a numerical range is indicated herein, it is meant to include any mentioned number (fraction or integer) contained within the indicated range. The expression "range / between" the first indicated number and the second indicated number, and the first indicated number "from" to the second indicated number ". The expression "range to / to" is used interchangeably and is meant to include the first indicated number, the second indicated number, and all fractions and integers in between.

Throughout the specification, the term "(meth) acrylic" includes acrylic and methacrylic compounds.

Throughout the specification, the expression "linking moiety" or "linking group" describes a group connecting two or more moieties or groups in a compound. The linking moiety is generally derived from a bi- or trifunctional compound and can be considered as two or three radical moieties, with the two or three radicals via their two or three atoms, respectively. Connected to two or three other parts.

Exemplary linking moieties, as described herein, are as follows, as defined as hydrocarbon moieties or chains and / or linking groups that are optionally interrupted by one or more heteroatoms. Includes any of the chemical groups listed in.

When a chemical group is referred to herein as a "terminal group", it is interrupted as a substituent and the substituent is attached to another group by one of its atoms.

Throughout the specification, the term "hydrocarbon" collectively describes chemical groups composed primarily of carbon and hydrogen atoms. Hydrocarbons can consist of alkyl, alkene, alkyne, aryl, and / or cycloalkyl, each of which may or may not be substituted and may be interrupted by one or more heteroatoms. The number of carbon atoms is in the range of 2 to 20, preferably lower, and can be, for example, 1 to 10, or 1 to 6, or 1 to 4. Hydrocarbons can be linking or terminal groups.

Bisphenol A is an example of a hydrocarbon composed of two aryl groups and one alkyl group.

As used herein, the term "amine" describes both the -NR'R "group and the -NR'-group, where R'and R" are independently hydrogen, alkyl, cycloalkyl, respectively. Or aryl, these terms are defined below herein.

Thus, the amine group is a primary amine (where both R'and R'are hydrogen), a secondary amine (where R'is hydrogen and R'is alkyl, cycloalkyl, or aryl. , Or tertiary amines (where R'and R'are independently alkyl, cycloalkyl or aryl, respectively).

Alternatively, R'and R'are independent hydroxyalkyl, trihaloalkyl, cycloalkyl, alkenyl, alkynyl, aryl, heteroaryl, heterolipid rings, amines, halides, sulfonates, sulfoxides, phosphonates, hydroxys, alkoxys, respectively. , Aryloxy, thiohydroxy, thioalkoxy, thioaryloxy, cyano, nitro, azo, sulfoxide, carbonyl, C-carboxylate, O-carboxylate, N-thiocarbamate, O-thiocarbamate, urea, thiourea, It can be N-carbamate, O-carbamate, C-amide, N-amide, guanyl, guanidine, or hydrazine.

The term "amine" is used herein to represent an -NR'R "group, as defined below herein when the amine is a terminal group, and the amine is also used. Used herein to represent a -NR'-group if it is part of a linking group or linking moiety.

The term "alkyl" refers to saturated aliphatic hydrocarbons containing straight chain and branched chain groups. Preferably, the alkyl group has 1 to 3 or 1 to 20 carbon atoms. Whenever a numerical range, eg, "1-20", is mentioned herein, it is a carbon atom with one group (in this case an alkyl group), two carbon atoms, three carbon atoms, etc. It means that it contains up to 20 carbon atoms. The alkyl group can be substituted or unsubstituted. The substituted alkyl can have one or more substituents, each substituent independently, for example, hydroxyalkyl, trihaloalkyl, cycloalkyl, alkenyl, alkynyl, aryl, heteroaryl, heterolipid ring, etc. Amine, halide, sulfonate, sulfoxide, phosphonate, hydroxy, alkoxy, aryloxy, thiohydroxy, thioalkoxy, thioaryloxy, cyano, nitro, azo, sulfonamide, C-carboxylate, O-carboxylate, N-thiocarbamate , O-thiocarbamate, urea, thiourea, N-carbamate, O-carbamate, C-amide, N-amide, guanyl, guanidine, or hydrazine.

An alkyl group is a terminal group attached to a single adjacent atom (as the term is defined above herein), or two or more components via at least two carbons in its chain. Can be a linking group (the term is as defined above herein). When alkyl is the linking group, it is also referred to herein as "alkylene" or "alkylene chain".

As defined herein, C (1-4) alkyl substituted with a hydrophilic group is included herein under the expression "hydrophilic group".

Alkenes and alkynes as used herein are alkyls as defined herein, each containing one or more double or triple bonds.

The term "cycloalkyl" group describes an all-carbon monocyclic or fused ring (ie, a ring that shares an adjacent carbon atom pair) group in which one or more of the rings do not have a fully conjugated π-electron system. do. Examples include, but are not limited to, cyclohexane, adamatine, norbornyl, isobornyl, and analogs thereof. The cycloalkyl group can be substituted or unsubstituted. The substituted cycloalkyl can have one or more substituents, each substituent independently, for example, hydroxyalkyl, trihaloalkyl, cycloalkyl, alkenyl, alkynyl, aryl, heteroaryl, heterolipid ring. , Amine, halide, sulfonate, sulfoxide, phosphonate, hydroxy, alkoxy, aryloxy, thiohydroxy, thioalkoxy, thioaryloxy, cyano, nitro, azo, sulfonamide, C-carboxylate, O-carboxylate, N-thio It can be carbamate, O-thiocarbamate, urea, thiourea, N-carbamate, O-carbamate, C-amide, N-amide, guanyl, guanidine, or hydrazine. A cycloalkyl group is a terminal group attached to a single adjacent atom (as the term is defined above herein), or two or more via at least two carbons in its chain. It can be a linking group that links the components (this term is as defined above herein).

As defined herein, cycloalkyls of 1 to 6 carbon atoms substituted by two or more hydrophilic groups are included herein under the expression "hydrophilic groups".

The term "complex alicyclic" group describes a monocyclic or fused ring group having one or more atoms in the ring (s), for example nitrogen, oxygen and sulfur. The ring can also have one or more double bonds. However, the ring does not have a fully conjugated π-electron system. Representative examples are piperidine, piperazine, tetrahydrofuran, tetrahydropyran, morpholino and their analogs.

The complex alicyclic group can be substituted or unsubstituted. The substituted complex alicyclic can have one or more substituents, each substituent independently, for example, hydroxyalkyl, trihaloalkyl, cycloalkyl, alkenyl, alkynyl, aryl, heteroaryl, complex fat. Ring, amine, halide, sulfonate, sulfoxide, phosphonate, hydroxy, alkoxy, aryloxy, thiohydroxy, thioalkoxy, thioaryloxy, cyano, nitro, azo, sulfonamide, C-carboxylate, O-carboxylate, N- It can be thiocarbamate, O-thiocarbamate, urea, thiourea, N-carbamate, O-carbamate, C-amide, N-amide, guanyl, guanidine, or hydrazine. A complex alicyclic group is two or more via a terminal group attached to a single adjacent atom (as the term is defined above herein), or at least two carbons in its chain. Can be a linking group that links the components of (this term is as defined above herein).

A complex alicyclic group containing one or more electron donating atoms such as nitrogen or oxygen and having a numerical ratio of carbon atom to complex atom of 5: 1 or lower is referred to herein as a "hydrophilic group". Included below.

The term "aryl" group describes an all-carbon monocyclic or condensed polycyclic (ie, ring sharing adjacent carbon atom pairs) group having a fully conjugated π-electron system. Aryl groups can be substituted or unsubstituted. The substituted aryl can have one or more substituents, each substituent independently, for example, hydroxyalkyl, trihaloalkyl, cycloalkyl, alkenyl, alkynyl, aryl, heteroaryl, heterolipid ring, etc. Amine, halide, sulfonate, sulfoxide, phosphonate, hydroxy, alkoxy, aryloxy, thiohydroxy, thioalkoxy, thioaryloxy, cyano, nitro, azo, sulfonamide, C-carboxylate, O-carboxylate, N-thiocarbamate , O-thiocarbamate, urea, thiourea, N-carbamate, O-carbamate, C-amide, N-amide, guanyl, guanidine, or hydrazine. Aryl groups are terminal groups attached to a single adjacent atom (as the term is defined above herein), or two or more components via at least two carbons in its chain. Can be a linking group (the term is as defined above herein).

The term "heteroaryl" group is a monocyclic group or group having one or more atoms on the ring (s), such as nitrogen, oxygen and sulfur, and further having a fully conjugated π-electron system. Fused rings (ie, rings sharing adjacent carbon atom pairs) groups are described. Non-limiting examples of heteroaryl groups include pyrrole, furan, thiophene, imidazole, oxazole, thiazole, pyrazole, pyridine, pyrimidine, quinoline, isoquinoline and purine. Heteroaryl groups can be substituted or unsubstituted. Substituted heteroaryls can have one or more substituents, each substituent independently, eg, hydroxyalkyl, trihaloalkyl, cycloalkyl, alkenyl, alkynyl, aryl, heteroaryl, heterolipid ring. , Amine, halide, sulfonate, sulfoxide, phosphonate, hydroxy, alkoxy, aryloxy, thiohydroxy, thioalkoxy, thioaryloxy, cyano, nitro, azo, sulfonamide, C-carboxylate, O-carboxylate, N-thio It can be carbamate, O-thiocarbamate, urea, thiourea, N-carbamate, O-carbamate, C-amide, N-amide, guanyl, guanidine, or hydrazine. A heteroaryl group is a terminal group attached to a single adjacent atom (as the term is defined above herein), or two or more via at least two carbons in its chain. It can be a linking group that links the components (this term is as defined above herein). Typical examples are pyridine, pyrrole, oxazole, indole, purines and their analogs.

The terms "halide" and "halo" refer to fluorine, chlorine, bromine, or iodine.

The term "haloalkyl" describes an alkyl group as defined above, further substituted with one or more halides.

The term "sulfate" is an -OS (= O) ₂ -OR'terminal group or an -OS (= O) ₂ -O-linking group (these terms are as defined above herein). (In the formula, R'is as defined above in the present specification).

The term "thiosulfate" is an -OS (= S) (= O) -OR'terminal group or an -OS (= S) (= O) -O-linking group (these terms are herein). As defined above in the document) (in the formula, R'is as defined above in the present specification).

The term "sulfite" is an -OS (= O) -OR'terminal group or an -OS (= O) -O-linking group (these terms are defined above herein. (As defined above in the formula, R'is as defined above).

The term "thiosulfite" is an -OS (= S) -OR'terminal group or an -OS (= S) -O-linking group (these terms are defined above herein. (As defined above in the formula, R'is as defined above).

The term "sulfinate" is an -S (= O) -OR'terminal group or an -S (= O) -O-linking group (these terms are as defined above herein) (in the formula). , R'as defined above in this specification).

The terms "sulfoxide" or "sulfinyl" are -S (= O) R'terminal groups or -S (= O) -linking groups (these terms are as defined above herein) (formula). Where R'is as defined above in the present specification).

The term "sulfonate" is an -S (= O) ₂ -R'terminal group or an -S (= O) ₂ -linking group (these terms are as defined above herein) (in the formula). , R'as defined above in this specification).

The term "S-sulfonamide" is an -S (= O) ₂ -NR'R "terminal group or an -S (= O) ₂ -NR'-linking group (these terms are defined above herein. (In the formula, R'and R "are as defined above herein).

The term "N-sulfonamide" is an R'S (= O) ₂ -NR "terminal group or -S (= O) ₂ -NR'-linking group (these terms are defined above herein. As defined above) (in the formula, R'and R "are as defined above in the present specification).

The term "disulfide" is an -S-SR'terminal group or SS-linking group (these terms are as defined above herein) (in the formula, R'is the above herein. As defined in).

The term "phosphonate" is a -P (= O) (OR') (OR ") terminal group or -P (= O) (OR') having R'and R'as defined herein. (O) -Represents a linking group (these representations are as defined above herein).

The term "thiophosphonate" is a -P (= S) (OR') (OR ") terminal group or -P (= S) (OR) having R'and R'as defined herein. ') (O) -represents a linking group (these representations are as defined above herein).

The term "phosphinyl" refers to a -PR'R "terminal group or a -PR'-linking group having R'and R'as defined above herein (these representations are herein above. As defined in).

The term "phosphine oxide" has a -P (= O) (R') (R ") terminal group or -P (= O) (R'" having R'and R'as defined herein. )-Represents a linking group (these representations are as defined above herein).

The term "phosphine sulfide" has a -P (= S) (R') (R ") terminal group or -P (= S) (R'" having R'and R'as defined herein. )-Represents a linking group (these representations are as defined above herein).

The term "phosphite" is an -O-PR'(= O) (OR ") end group or -O-PH (= O) (O) having R'and R'as defined herein. )-Represents a linking group (these representations are as defined above herein).

The term "carbonyl" or the term "carbonate", as used herein, has an R'as defined herein-C (= O) -R' end group or -C ( = O) -represents a linking group (these representations are as defined above herein).

The term "thiocarbonyl", when used herein, has an R'as defined herein-C (= S) -R' end group or -C (= S)-. Represents a linking group (these representations are as defined above herein).

The term "oxo" as used herein represents an (= O) group, in which case the oxygen atom is linked to the atom at the indicated position (eg, a carbon atom) by a double bond. To.

The term "thiooxo" as used herein represents a (= S) group, in which case the sulfur atom is linked to the atom at the indicated position (eg, a carbon atom) by a double bond. Sulfur.

The term "oxime" describes a = N-OH end group or = NO-linking group (these terms are as defined above herein).

The term "hydroxyl" describes a -OH group.

The term "alkoxy" describes both the -O-alkyl group and the -O-cycloalkyl group as defined herein.

The term "aryloxy" describes both -O-aryl groups and -O-heteroaryl groups as defined herein.

The term "thiohydroxy" describes a -SH group.

The term "thioalkoxy" describes both -S-alkyl and -S-cycloalkyl groups as defined herein.

The term "thioaryloxy" describes both -S-aryl groups and -S-heteroaryl groups as defined herein.

"Hydroxyalkyl" is also referred to herein as "alcohol" and describes the alkyl defined herein that is substituted with a hydroxy group.

The term "cyano" describes the -C≡N group.

The term "isocyanate" describes an -N = C = O group.

The term "isothiocyanate" describes the -N = C = S group.

The term "nitro" describes _two -NOs.

The term "acyl halide" describes a-(C = O) R "" group (where R "" in the formula is a halide as defined above herein).

The terms "azo" or "diazo" are -N = NR'terminal groups or -N = N-linked groups (these terms are as defined above herein) (in the formula, R'is As defined above in this specification).

The term "peroxo" is an -O-OR'terminal group or an -O-O-linking group (these terms are as defined above herein) (in the formula, R'is in the present specification. As defined above).

The term "carboxylate" as used herein includes C-carboxylate and O-carboxylate.

The term "C-carboxylate" is a -C (= O) -OR'terminal group or an -C (= O) -O-linking group (these terms are as defined above herein). (In the formula, R'is as defined above in the present specification).

The term "O-carboxylate" is an -OC (= O) R'terminal group or an -OC (= O) -linking group (these terms are as defined above herein) (in the formula). , R'as defined above in this specification).

The carboxylate can be linear or cyclic. When cyclic, R'and carbon atoms are linked together to form a ring with C-carboxylate, which group is also designated as a lactone. Alternatively, R'and O are linked together to form a ring at O-carboxylate. The cyclic carboxylate can function as a linking group, for example, when an atom in the formed ring is linked to another group.

The term "thiocarboxylate", as used herein, includes C-thiocarboxylate and O-thiocarboxylate.

The term "C-thiocarboxylate" is a -C (= S) OR'terminal group or an -C (= S) -O-linking group (these terms are as defined above herein). (In the formula, R'is as defined above in the present specification).

The term "O-thiocarboxylate" is an -OC (= S) R'terminal group or an -OC (= S) -linking group (these terms are as defined above herein) (formula. Where R'is as defined above in the present specification).

The thiocarboxylate can be linear or cyclic. When cyclic, R'and carbon atoms are linked together to form a ring with C-thiocarboxylate, the group of which is also designated as thiolactone. Alternatively, R'and O are linked together to form a ring with O-thiocarboxylate. Cyclic thiocarboxylate can function as a linking group, for example, when an atom in the formed ring is linked to another group.

The term "curvamate" as used herein includes N-carbamate and O-carbamate.

The term "N-carbamate" is an R "OC (= O) -NR'-terminal group or -OC (= O) -NR'-linking group, as these terms are defined above herein. Are) (in the formula, R'and R "are as defined above herein).

The term "O-carbamate" refers to the -OC (= O) -NR'R "terminal group or the -OC (= O) -NR'-linking group, as these terms are defined above herein. Are) (in the formula, R'and R "are as defined above herein).

Carbamate can be linear or cyclic. When cyclic, R'and carbon atoms are linked together to form a ring with O-carbamate. Alternatively, R'and O are linked together to form a ring with N-carbamate. Cyclic carbamate can function as a linking group, for example, when an atom in the formed ring is linked to another group.

The term "curvamate" as used herein includes N-carbamate and O-carbamate.

The term "thiocarbamate" as used herein includes N-thiocarbamate and O-thiocarbamate.

The term "O-thiocarbamate" is a -OC (= S) -NR'R "terminal group or a -OC (= S) -NR'-linking group (these terms are as defined above herein). (In the formula, R'and R "are as defined above herein).

The term "N-thiocarbamate" is an R "OC (= S) NR'-terminal group or -OC (= S) NR'-linking group (these terms are as defined above herein. ) (In the formula, R'and R "are as defined above herein).

The thiocarbamate can be linear or cyclic, as described herein for carbamate.

The term "dithiocarbamate" as used herein includes S-dithiocarbamate and O-thiodithiocarbamate.

The term "S-dithiocarbamate" is a -SC (= S) -NR'R "terminal group or a -SC (= S) NR'-linking group, as these terms are defined above herein. Are) (in the formula, R'and R "are as defined above herein).

The term "N-dithiocarbamate" is an R "SC (= S) NR'-terminal group or -SC (= S) NR'-linking group (these terms are as defined above herein. ) (In the formula, R'and R "are as defined above herein).

The term "urea" (also referred to as "ureido") is a -NR'C (= O) -NR "R"'terminal group or -NR'C (= O) -NR "-linking group (these terms). As defined above herein) (in the formula, R'and R "as defined above herein, R"'is R'and R "as defined herein. As defined in).

The term "thiourea" (also referred to as "thioureid") is a -NR'C (= S) -NR "R"'terminal group or -NR'-C (= S) -NR "-linking group (these). The terminology is as defined above herein) (where R', R "and R"'are defined above herein in the formula).

The term "amide", as used herein, includes C-amides and N-amides.

The term "C-amide" is a -C (= O) -NR'R "terminal group or a -C (= O) -NR'-linking group, as these terms are defined above herein. Are) (in the formula, R'and R "are as defined above herein).

The term "N-amide" is an R'C (= O) -NR "-terminal group or R'C (= O) -N-linked group (these terms are as defined above herein. Are) (in the formula, R'and R "are as defined above herein).

The amide can be linear or cyclic. When cyclic, R'and carbon atoms are linked together to form a ring with C-amide, the group of which is also designated as a lactam. Cyclic amides can function as linking groups, for example, when the atoms in the formed ring are linked to another group.

The term "guanyl" is an R'R "NC (= N) -terminal group or -R'NC (= N) -linked group (these terms are as defined above herein) (formula. , R'and R "as defined above herein).

The term "guanidine" is a -R'NC (= N) -NR "R"'terminal group or a -R'NC (= N) -NR "-linking group (these terms are defined above herein. (In the formula, R', R "and R"'are as defined above in the present specification).

The term "hydrazine" is a -NR'-NR "R"'terminal group or -NR'-NR "-linking group (these terms are as defined above herein) (in the formula, R. ', R'and R''are as defined above herein).

As used herein, the term "hydrazide" is as R', R "and R"'are defined herein-C (= O) -NR'-NR "R. Represents a "'terminal group or -C (= O) -NR'-NR" -linking group (these representations are as defined above herein).

As used herein, the term "thiohydrazide" is as R', R "and R"'are defined herein-C (= S) -NR'-NR ". Represents an R "'terminal group or -C (= S) -NR'-NR" -linking group (these representations are as defined above herein).

As used herein, the term "alkylene glycol" is -O-[(CR'R ") _z -O] _y -R"'terminal group or -O-[(CR'R ") _z- O] _y -represents a linking group, where R', R "and R"'are as defined herein and z is an integer of 1-10, preferably 2-10. It is an integer of 6, more preferably an integer of 2 or 3, y is an integer of 1 or more, preferably both R'and R'are hydrogen. When z is 2 and y is 1, this group is ethylene glycol. When z is 3 and y is 1, this group is propylene glycol. When y is 2-4, the alkylene glycol is referred to herein as an oligo (alkylene glycol).

When y is greater than 4, this alkylene glycol is referred to herein as poly (alkylene glycol). In some embodiments of the invention, the poly (alkylene glycol) group or poly (alkylene glycol) moiety has a z of 1 to 200, preferably 1 to 100, more preferably 10 to 100. It is possible to have 1 to 20 repeating alkylene glycol units such as 50.

The term "silanol" describes an -Si (OH) R'R "group or an -Si (OH) ₂ R'group or an -Si (OH) ₃ group, where R'and R" are defined herein. As it is done.

The term "silyl" describes the -SiR'R "R"'group, as R', R "and R"'as defined herein.

As used herein, the term "urethane" or "urethane moiety" or "urethane group" is the RX-OC (= O) -NR'R "terminal group or _{-RX -} OC. (= O) NR'linking groups are described, _R'and R'are as defined herein and RX is an alkyl, cycloalkyl, aryl, alkylene glycol or any combination thereof. be. Preferably, both R'and R'are hydrogen.

The term "polyurethane" or "oligourethane" comprises at least one urethane group as described herein in the repeating backbone unit, or a urethane bond-OC (= O) in the repeating backbone unit. The part containing at least one NR'-is described.

It will be appreciated that certain features of the invention, described in the context of separate embodiments for clarity, can also be provided in combination in a single embodiment. Conversely, the various features of the invention described in a single embodiment for brevity are provided separately or in appropriate subcombinations, or as suitable in other described embodiments of the invention. You can also do it. Certain features described in the context of the various embodiments should not be considered an integral feature of those embodiments unless the embodiment is inoperable without those elements. ..

Experimental support is found in the examples below for each of the various embodiments and embodiments of the invention as depicted above herein and as claimed in the claims below. ..

The following examples will then be referred to, which, along with the above description, illustrate the invention in a non-limiting manner.

Experimental Method Shore A hardness was determined according to ASTM D2240.

The modulus of elasticity (elastic modulus) was determined from the strength-strain curve according to ASTM D412.

Tensile strength was determined according to ASTM D412.

The Z tensile strength was determined according to ASTM D412 when printing in the Z direction.

Elongation was determined according to ASTM D412.

The Z elongation was determined according to ASTM D412 when printing in the Z direction.

Tear resistance (TR) was determined according to ASTM D624.

The O-ring tear test was performed as depicted in FIGS. 6A-C and the time to destruction of the tested object was measured.

In particular, as depicted in FIG. 6A, it comprises two O-rings connected by a tube and has a neck length: 50 mm; X length: 110 mm; Y length: 30 mm; Z length: 10 mm. Objects with dimensions are stretched using the stretching device depicted in FIG. 6B, as depicted in FIG. 6C. The time it takes for a model to be stretched before it breaks is measured and represents the "static" tear resistance, that is, the resistance to static tension in the stretched state (lower than the stretch at break).

Prior to the measurement being performed, the printed object (typically a mat printed in HS (high speed) mode) was washed with water using a jet station, condition adjusted and dried in laboratory conditions for 24 hours. Receive.

3D inkjet printing was performed using a Triplex / C500 3D inkjet printing system operated in HS mode, unless otherwise indicated.

The mold preparation was obtained according to ASTM412. Simply put, a silicone mold with dimensions according to ASTM412 was used. The compound tested was poured into the mold and a silicon film was used to cover the mold. The formulation was cured at room temperature in a UV chamber for 3 hours and the test was then gently removed from the mold. After 24 hours, the test was measured according to ASTM D412.

Formulations were prepared by mixing all ingredients at room temperature, unless otherwise indicated. Powder components such as photoinitiators were dissolved at 85 ° C. for 30 minutes.

The "Mill base" formulation grinds / disperses silica in one of the curable monomers at a high concentration (eg, at a concentration of about 20% by weight or about 25% by weight), thereby "paste pigment". Was then prepared by adding a paste pigment to the formulation to achieve the final concentration as shown.

Results Table 1 below is used to provide a soft rubber material characterized by a Shore A hardness of about 27 by 3D inkjet printing, as Reference A, also as a reference formulation referred to herein, Elastomer A. Printed on a Triplex / C500 3D inkjet printing system operated in HS mode using the components of the soft rubber material according to the exemplary embodiments of the invention referred to herein, and their respective formulations. Gives the mechanical properties of an elastomer.

Table 2 is used herein by 3D inkjet printing to provide a hard rubber material characterized by a Shore A hardness of about 60, which is also referred to herein as Reference Formulation B, Elastomer B. Ingredients of a hard rubber material according to an exemplary embodiment of the invention referred to in, and objects printed by a Triplex / C500 3D inkjet printing system operated in HS mode using their respective formulations. Gives mechanical properties.

Additional formulations containing similar ingredients and different types of silica at different concentrations were prepared and tested.

All formulations contained Elastomer A, reactive and non-reactive components (excluding silica R7200) as described herein for Table 1, and the following silica nanoparticles were used:

Silica R7200, which is also referred to in the industry as AEROSIL® R7200, is a methacrylate-functionalized fumed silica. Silica R7200 is an exemplary hydrophobic reactive silica according to this embodiment.

Colloidal silica and silica nanopowder are exemplary hydrophilic silicas. The colloidal silica used herein was obtained as silica particles dispersed in a monofunctional curable material.

Silica nanoparticles (10-20 nm particle size) were obtained from Sigma (Cat No. 637238).

Silica R8200, which is also referred to in the industry as AEROSIL® R8200, is an exemplary hydrophobic silica according to this embodiment.

Table 3 below gives data obtained for objects made in the mold from the tested formulations and printed objects made from each of the formulations as described above.

Table 4 below is a comparison of the formulations shown as Reference A (see Table 1) and printed objects made from the same formulations with the addition of 4% to 10% (weight) of colloidal silica. Gives mechanical properties.

FIG. 7 shows a 3D inkjet printed object made from each of the various concentrations of hydrophobic, acrylic coated fumed silica, silica R7200 when added to the rubbery material formulation given as Reference A. Gives an effect on the stress-strain curve.

FIG. 8 shows hydrophobicity, acrylic coated fumed silica, silica R7200, and 10% (hydrophilic) colloidal silica when added to the rubbery material formulation shown as "T" and given as Reference A. It provides effects on stress-strain curves of 3D inkjet printed objects made from the respective formulations at various concentrations.

FIG. 9 shows a water pipe connector (left tube) printed using an exemplary formulation according to some embodiments of the invention, after fitting into the water pipe for 10 hours, and a silica-free formulation. Give a printed water pipe connector (the pipe on the right) using an object. As shown, the silica-free elastomer moiety was torn after 10 hours and the silica-containing moiety remained intact and retained for several weeks (data not shown).

The data given here are submicron such as (acrylic functionalized) fumed silica or colloidal silica in amounts up to 15% by weight in UV curable formulations used to produce elastomers by 3D printing. It is shown that the use of silica improves the mechanical properties of the printed part.

A particularly significant improvement is shown in the tear resistance of the printed rubbery object.

Printed acrylic elastomers are generally extremely sensitive to tearing. For example, in Polyjet (trade name) printing, the printed fine portions made of acrylic elastomer are often torn when the support is removed by water injection. Parts that undergo constant elongation when used are also often torn after a few minutes to hours.

When fine silica particles are added to the formulation, the tear resistance under constant elongation is increased from minutes to days without impairing elongation. See, for example, Table 1-4.

In addition to improving the tear resistance of printed articles, the addition of silica particles does not affect or even increase the elongation of the printed object; for example, a two-fold or even three-fold improvement in modulus. Bringing; and / or resulting in a reduction in the surface tackiness of the printed object without substantially compromising other mechanical properties.

Both hydrophobic and hydrophilic silicas have similar effects, and more substantial improvements have been shown for hydrophobic silicas, especially acrylic functionalized silicas. It is probably the result of an interaction with the acrylic monomer in the formulation.

Although the present invention has been described by its particular embodiment, it will be apparent to those skilled in the art that there are many alternatives, modifications and variations. Accordingly, the present invention embraces all such alternatives, modifications and modifications that fall within the spirit and scope of the claims of the present application.

All publications, patents and patent applications cited herein are herein in their entirety to the same extent that individual publications, patents and patent applications are individually cited and presented as if each were specifically and individually cited. It is to be used for. Furthermore, what is cited or confirmed in this application should not be regarded as a confession that it can be used as the prior art of the present invention. To the extent that section headings are used, they should not necessarily be construed as limiting.

Claims (42)

A method of additional manufacturing of a three-dimensional object made of an elastomeric material, said method comprising sequentially forming multiple layers in a forming pattern corresponding to the shape of the object, thereby forming the object.
The formation of the layer comprises ejecting at least one form material formulation and exposing the ejected form material to curing energy to form a cured form material.
The at least one modeling material formulation comprises an elastomeric curable material and silica particles.
The addition manufacturing is 3D inkjet printing.
The elastomer curable material is a UV curable acrylic elastomer.
The curing energy includes UV irradiation and
A method in which the weight ratio of the elastomeric curable material to the silica particles is in the range of 30: 1 to 4: 1. The method of claim 1, wherein the silica particles have an average particle size smaller than 1 micron. The method according to claim 1 or 2, wherein at least a part of the silica particles has a hydrophilic surface. The method according to claim 1 or 2, wherein at least a part of the silica particles has a hydrophobic surface. The method according to any one of claims 1, 2 and 4, wherein at least a part of the silica particles contains functionalized silica particles. The method of claim 5, wherein at least a portion of the silica particles is functionalized with a curable functional group. The method of claim 6, wherein the curable functional group comprises a (meth) acrylate group. The method according to any one of claims 1 to 7, wherein the amount of the silica particles in the modeling material formulation is in the range of 1 to 20% by weight of the total weight of the modeling material formulation containing the particles. The method according to any one of claims 1 to 8, wherein the amount of the elastomeric curable material is at least 40 % by weight of the total weight of the modeling material formulation containing the material. The method according to any one of claims 1 to 9, wherein the elastomeric curable material and the silica particles are in the same modeling material formulation. The method according to any one of claims 1 to 10, wherein the at least one modeling material formulation further comprises at least one additional curable material. 11. The method of claim 11, wherein the elastomeric curable material, the silica particles, and the additional curable material are in the same modeling material formulation. The discharge is of at least two modeling material formulations, one of which comprises the elastomeric curable material and another of which comprises the additional curable material. The method according to claim 11. The method according to any one of claims 1 to 13, wherein the at least one modeling material formulation further comprises at least one additional non-curable material. The method according to any one of claims 1 to 14, wherein the at least one modeling material formulation is characterized by a tear resistance of at least 4000 N / m when cured. 13. the method of. The method according to any one of claims 1 to 16, wherein the at least one modeling material formulation is characterized by a tensile strength of at least 2 MPa when cured. A compounding system comprising an elastomeric curable material and at least one additional curable material and silica particles, wherein the compounding system comprises one or more formulations.
The elastomer curable material is a UV curable acrylic elastomer.
A compounding system in which the weight ratio of the total weight of the elastomer curable material to the total weight of the silica particles is in the range of 30: 1 to 4: 1. The compounding system according to claim 18 , wherein the silica particles have an average particle size smaller than 1 micron. The compounding system according to claim 18 or 19 , wherein at least a part of the silica particles has a hydrophilic surface. The compounding system of claim 18 or 19 , wherein at least a portion of the silica particles comprises a hydrophobic surface. The compounding system according to any one of claims 18 , 19 and 21 , wherein at least a part of the silica particles contains functionalized silica particles. 22. The compounding system of claim 22 , wherein at least a portion of the silica particles is functionalized with a curable functional group (eg, a (meth) acrylate group). The compounding system according to claim 23 , wherein the curable functional group contains a (meth) acrylate group. The compounding system according to any one of claims 18 to 24 , wherein the amount of the silica particles in the compounding system is in the range of 1 to 20% by weight. The compounding system according to any one of claims 18 to 25 , wherein the amount of the elastomeric curable material in the compounding system is at least 40 % by weight. The compounding system according to any one of claims 18 to 26 , wherein the elastomeric curable material and the silica particles are contained in the same compound. The compounding system according to any one of claims 18 to 27 , wherein the elastomeric curable material, the silica particles, and the additional curable material are in the same formulation. The formulation system of any of claims 18-27, comprising at least two formulations, wherein one of the formulations comprises an elastomeric curable material and another type of formulation comprises the additional cure. The compounding system according to any one of claims 18 to 27 , which comprises a sex material. The compounding system of any of claims 18-29 , further comprising at least one additional non-curable material. The compounding system of any of claims 18-30 , comprising at least one elastomer monofunctional curable material, at least one elastomer polyfunctional curable material, and at least one additional monofunctional curable material. The compounding system according to claim 31 , wherein the total concentration of the monofunctional curable material is in the range of 10 to 30% by weight. The compounding system according to claim 31 or 32 , wherein the total concentration of the elastomer monofunctional curable material is in the range of 50 to 70% by weight. The compounding system according to any one of claims 31 to 33 , wherein the total concentration of the elastomer polyfunctional curable material is in the range of 10 to 20% by weight. The compounding system according to claim 31 , wherein the total concentration of the monofunctional curable material is in the range of 20 to 30% by weight. The compounding system according to claim 31 or 35 , wherein the total concentration of the elastomer monofunctional curable material is in the range of 30 to 50% by weight. The compounding system according to any one of claims 31 , 35 and 36 , wherein the total concentration of the elastomer polyfunctional curable material is in the range of 10 to 30% by weight. The compounding system according to any one of claims 18 to 37 , which is used for additional manufacturing of a three-dimensional object. A kit comprising the compounding system according to any one of claims 18 to 38 . The compounding system of any of claims 18-38 , which, when cured, provides a material characterized by a tear resistance of at least 4000 N / m. The compounding system of any of claims 18-38 and 40 , which, when cured , provides a material characterized by a tear resistance that is at least 500 N / m higher than the cured material without silica particles. The compounding system of any of claims 18-38 , 40 and 41 , which, when cured, provides a material characterized by a tensile strength of at least 2 MPa.

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